U.S. patent application number 11/703806 was filed with the patent office on 2007-07-26 for polypropylene resin compositions.
Invention is credited to Markus Blomenhofer, Hans-Werner Schmidt, Paul Smith.
Application Number | 20070170398 11/703806 |
Document ID | / |
Family ID | 22951789 |
Filed Date | 2007-07-26 |
United States Patent
Application |
20070170398 |
Kind Code |
A1 |
Schmidt; Hans-Werner ; et
al. |
July 26, 2007 |
Polypropylene resin compositions
Abstract
A polypropylene composition containing the components a) a
crystallizable polypropylene homopolymer, random copolymer,
alternating or segmented copolymer, block copolymer or a blend of
polypropylene with another synthetic polymer, and b) 0.001 to 5%,
relative to the weight of component a), of a specific trimesic acid
derivative.
Inventors: |
Schmidt; Hans-Werner;
(Bayreuth, DE) ; Smith; Paul; (Zurich, CH)
; Blomenhofer; Markus; (Bayreuth, DE) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION;PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
22951789 |
Appl. No.: |
11/703806 |
Filed: |
February 7, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10433512 |
Jun 3, 2003 |
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PCT/EP01/13791 |
Nov 27, 2001 |
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11703806 |
Feb 7, 2007 |
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60251396 |
Dec 6, 2000 |
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Current U.S.
Class: |
252/401 ;
524/210 |
Current CPC
Class: |
C08L 23/10 20130101;
C08L 55/02 20130101; C08L 55/02 20130101; C08K 5/20 20130101; C08L
2666/24 20130101; C08L 2666/04 20130101; C08L 2666/24 20130101;
C08L 23/10 20130101; C08L 2666/04 20130101; C08L 2666/24 20130101;
C08L 2666/24 20130101; C08L 2666/04 20130101; C08L 2666/04
20130101; C08L 2666/24 20130101; C08L 2666/04 20130101; C08L 53/00
20130101; C08L 51/003 20130101; C08L 51/003 20130101; C08L 101/00
20130101; C08L 55/02 20130101; C08L 23/10 20130101; C08L 23/10
20130101; C08L 51/003 20130101; C08L 53/02 20130101; C08L 53/02
20130101; C08K 5/20 20130101; C08L 53/02 20130101; C08L 53/00
20130101; C08L 53/00 20130101 |
Class at
Publication: |
252/401 ;
524/210 |
International
Class: |
C09K 15/16 20060101
C09K015/16; C08K 5/00 20060101 C08K005/00 |
Claims
1. A polypropylene composition containing the components a) a
crystallizable polypropylene homopolymer, random copolymer,
alternating or segmented copolymer, block copolymer or a blend of
polypropylene with another synthetic polymer, and b) 0.001 to 5%,
relative to the weight of component a), of a compound of the
formula (I) ##STR9## wherein R.sub.1, R.sub.2 and R.sub.3,
independently of one another, are C.sub.1-C.sub.20alkyl,
C.sub.1-C.sub.20alkyl substituted by C.sub.1-C.sub.20alkylamino,
di(C.sub.1-C.sub.20alkyl)amino, C.sub.1-C.sub.20alkyloxy or
hydroxy; {poly(C.sub.2-C.sub.4alkoxy)}-(C.sub.2-C.sub.4alkyl),
C.sub.2-C.sub.20alkenyl, C.sub.3-C.sub.12cycloalkyl,
C.sub.3-C.sub.12cycloalkyl substituted by 1, 2 or 3
C.sub.1-C.sub.20alkyl; cyclohexylmethyl; cyclohexylmethyl
substituted by 1, 2 or 3 C.sub.1-C.sub.20alkyl;
C.sub.3-C.sub.12cycloalkenyl, C.sub.3-C.sub.12cycloalkenyl
substituted by 1, 2 or 3 C.sub.1-C.sub.20alkyl; phenyl, phenyl
substituted by 1, 2 or 3 radicals selected from the group
consisting of C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.20alkyloxy,
hydroxy, halogen, trihalogenmethyl, trihalogenmethoxy, benzoyl,
phenylamino, acylamino and phenylazo; phenyl substituted by 5
halogen, C.sub.7-C.sub.9phenylalkyl, C.sub.7-C.sub.9phenylalkyl
which is substituted on the phenyl by 1, 2 or 3 radicals selected
from the group consisting of C.sub.1-C.sub.20alkyl,
C.sub.1-C.sub.20alkoxy and hydroxy; naphthyl, naphthyl substituted
by C.sub.1-C.sub.20alkyl; adamantyl, adamantyl substituted by
C.sub.1-C.sub.20alkyl; or a 5 to 6 membered heterocyclic group;
characterized in that the polypropylene composition has a haze
value which is smaller than 62%; the haze value being measured at a
plate of 1.1-1.2 mm thickness.
2. A polypropylene composition according to claim 1 wherein
component a) is a polypropylene homopolymer.
3. A polypropylene composition according to claim 1 wherein
component a) is a polypropylene random copolymer, alternating or
segmented copolymer or block copolymer containing one or more
comonomers selected from the group consisting of ethylene,
C.sub.4-C.sub.20.alpha.-olefin, vinylcyclohexane, vinylcyclohexene,
C.sub.4-C.sub.20alkanediene, C.sub.5-C.sub.12cycloalkandiene and
norbornene derivatives.
4. A polypropylene composition according to claim 1 wherein
R.sub.1, R.sub.2 and R.sub.3 are identical.
5. A polypropylene composition according to claim 1 wherein R.sub.1
and R.sub.2 are identical and R.sub.3 is different from R.sub.1 and
R.sub.2.
6. A polypropylene composition according to claim 1 wherein
R.sub.1, R.sub.2 and R.sub.3, independently of one another, are
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.10alkyl substituted by
C.sub.1-C.sub.4alkylamino , di(C.sub.1-C.sub.4alkyl)amino or
C.sub.1-C.sub.4alkyloxy;
{poly(C.sub.2-C.sub.4alkoxy)}-(C.sub.2-C.sub.4alkyl),
C.sub.3-C.sub.18alkenyl, C.sub.5-C.sub.6cycloalkyl,
C.sub.5-C.sub.6cycloalkyl substituted by 1, 2 or 3
C.sub.1-C.sub.4alkyl; cyclohexylmethyl; cyclohexylmethyl
substituted by 1, 2 or 3 C.sub.1-C.sub.4alkyl; phenyl, phenyl
substituted by 1, 2 or 3 radicals selected from the group
consisting of C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkyloxy,
hydroxy, halogen, benzoyl, phenylamino,
C.sub.1-C.sub.4alkanoylamino and phenylazo; benzyl, benzyl which is
substituted on the phenyl by 1, 2 or 3 radicals selected from the
group consisting of C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy and
hydroxy; phenylethyl, phenylethyl which is substituted on the
phenyl by 1, 2 or 3 radicals selected from the group consisting of
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy and hydroxy; naphthyl,
naphthyl substituted by C.sub.1-C.sub.4alkyl; adamantyl, adamantyl
substituted by C.sub.1-C.sub.4alkyl; or a 5 to 6 membered
heterocyclic group.
7. A polypropylene composition according to claim 1 wherein R.sub.1
and R.sub.2, independently of one another, are
C.sub.3-C.sub.8alkyl, C.sub.5-C.sub.6cycloalkyl, cyclohexylmethyl,
C.sub.5-C.sub.6cycloalkyl substituted by 1, 2 or 3
C.sub.1-C.sub.4alkyl; or adamantyl.
8. A polypropylene composition according to claim 1 wherein
R.sub.1, R.sub.2 and R.sub.3, independently of one another, are
C.sub.3-C.sub.8alkyl, C.sub.5-C.sub.6cycloalkyl, cyclohexylmethyl,
C.sub.5-C.sub.6cycloalkyl substituted by 1, 2 or 3
C.sub.1-C.sub.4alkyl; or adamantyl.
9. A polypropylene composition according to claim 1 wherein
R.sub.1, R.sub.2 and R.sub.3 are identical and are isopropyl,
2-methylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl,
1,2-dimethylpropyl, n-butyl, 2-butyl, tert-butyl, 3-methylbutyl,
1,1,3,3-tetramethylbutyl, cyclobutyl, cyclopentyl, cyclohexyl,
2-methylcyclohexyl, 4-methylcyclohexyl, cyclohexylmethyl,
3,3,5-trimethylcyclohexyl or 1-adamantyl.
10. A polypropylene composition according to claim 1 wherein
R.sub.1, R.sub.2 and R.sub.3 are identical and are isopropyl,
2-methylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2-butyl,
tert-butyl, 3-methylbutyl, 1,1,3,3-tetramethylbutyl, cyclopentyl,
cyclohexyl, 2-methylcyclohexyl, cyclohexylmethyl or
1-adamantyl.
11. A polypropylene composition according to claim 1 wherein
R.sub.1, R.sub.2 and R.sub.3 are identical and are isopropyl,
2-butyl, tert-butyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl or
1-adamantyl.
12. A polypropylene composition according to claim 1 wherein
R.sub.1, R.sub.2 and R.sub.3 are identical and are
1,2-dimethylpropyl, tert-butyl, 3-methylbutyl,
1,1,3,3-tetramethylbutyl, cyclopentyl or cyclohexyl.
13. A polypropylene composition according to claim 1 wherein
R.sub.1, R.sub.2 and R.sub.3 are identical and are
1,2-dimethylpropyl, 3-methylbutyl or cyclopentyl.
14. A polypropylene composition according to claim 1; characterized
in that the polypropylene composition has a haze of 3 to 62%.
15. A polypropylene composition according to claim 1; characterized
in that the polypropylene composition has a haze of 3 to 50%.
16. A polypropylene composition according to claim 1; characterized
in that the polypropylene composition has a haze of 3 to 40%.
17. A polypropylene composition according to claim 1 containing as
additional component c) 0.001 to 5%, relative to the weight of
component a), of a conventional nucleating agent.
18. A method for providing a resin with a haze value which is
smaller than 62%; the haze value being measured at a plate of
1.1-1.2 mm thickness; said resin being selected from the group
consisting of a crystallizable polypropylene homopolymer, random
copolymer, alternating or segmented copolymer, block copolymer and
a blend of polypropylene with another synthetic polymer; which
method comprises incorporating into the resin 0.001 to 5%, relative
to the weight of the resin, of a compound of the formula (I)
according to claim 1.
19. A compound of the formula (IA) ##STR10## wherein R.sub.1 and
R.sub.2, independently of one another, are C.sub.1-C.sub.20alkyl,
C.sub.1-C.sub.20alkyl substituted by C.sub.1-C.sub.20alkylamino,
di(C.sub.1-C.sub.20alkyl)amino, C.sub.1-C.sub.20alkyloxy or
hydroxy; {poly(C.sub.2-C.sub.4alkoxy)}-(C.sub.2-C.sub.4alkyl),
C.sub.2-C.sub.20alkenyl, C.sub.3-C.sub.12cycloalkyl,
C.sub.3-C.sub.12cycloalkyl substituted by 1, 2 or 3
C.sub.1-C.sub.20alkyl; cyclohexylmethyl; cyclohexylmethyl
substituted by 1, 2 or 3 C.sub.1-C.sub.20alkyl;
C.sub.3-C.sub.12cycloalkenyl, C.sub.3-C.sub.12cycloalkenyl
substituted by 1, 2 or 3 C.sub.1-C.sub.20alkyl; phenyl, phenyl
substituted by 1, 2 or 3 radicals selected from the group
consisting of C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.20alkyloxy,
hydroxy, halogen, trihalogenmethyl, trihalogenmethoxy, benzoyl,
phenylamino, acylamino and phenylazo; phenyl substituted by 5
halogen, C.sub.7-C.sub.9phenylalkyl, C.sub.7-C.sub.9phenylalkyl
which is substituted on the phenyl by 1, 2 or 3 radicals selected
from the group consisting of C.sub.1-C.sub.20alkyl,
C.sub.1-C.sub.20alkoxy and hydroxy; naphthyl, naphthyl substituted
by C.sub.1-C.sub.20alkyl; adamantyl, adamantyl substituted by
C.sub.1-C.sub.20alkyl; or a 5 to 6 membered heterocyclic group; and
R.sub.3 is 2-ethylhexyl, 3-methyl-1-butyl, 3-(dimethylamino)propyl,
3-(diethylamino)propyl, 3-(methylamino)propyl, 2-(ethoxy)ethyl,
3-(methoxy)propyl, 3-(ethoxy)propyl, 2-picolyl, furfuryl,
tetrahydrofurfuryl, 2-pyrimidinyl, 4-(phenylamino)phenyl,
4-isopropylphenyl, 2-ethylphenyl, 2,4-diethylphenyl,
2-ethyl-6-methylphenyl, 2,6-diisopropylphenyl, 4-methoxyphenyl,
4-ethoxyphenyl, 1,2,4-triazol-3-yl or 4-(phenlyazo)phenyl.
20. A compound according to claim 19 wherein R.sub.1, R.sub.2 and
R.sub.3 are identical.
21. A compound of the formula (IB) ##STR11## wherein R.sub.1,
R.sub.2 and R.sub.3 are identical and are 3-methylphenyl,
2,3-dimethylphenyl, 2,4-dimethylphenyl, 3,4-dimethylphenyl,
2,4,6-trimethylphenyl, 2-ethylphenyl, 4-n-butylphenyl,
4-methoxyphenyl, 4-ethoxyphenyl, 4-(n-decyloxy)phenyl, cyclopropyl,
cyclobutyl, cycloheptyl, 1-adamantyl, 3-methylcyclohexyl,
2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl,
S(+)-1-cyclohexylethyl, R(+)-1-cyclohexylethyl, isopropyl,
1,1-dimethylpropyl, 1,2-dimethylpropyl, 2-butyl, 3-methylbutyl,
1,1,3,3-tetramethylbutyl, 3,5-difluorophenyl, pentafluorophenyl or
4-(trifluoromethoxy)phenyl.
22. A compound according to claim 21 wherein R.sub.1, R.sub.2 and
R.sub.3 are identical and are 1,2-dimethylpropyl, 3-methylbutyl or
1,1,3,3-tetramethylbutyl.
Description
[0001] This application is a continuation of U.S. application Ser.
No. 10/433,512, which is a 371 of PCT/EP 01/13791, filed Nov. 27,
2001, which claims benefit of U.S. provisional app. No. 60/251,396,
filed Dec. 6, 2000, the contents of which applications are
incorporated by reference.
[0002] The present invention relates to polypropylene resin
compositions having excellent crystallizability, high
transmittance, high clarity, low haze and improved thermal
stability, and containing trimesic acid derivatives, to the use of
these trimesic acid derivatives as haze reducing agents, to
mixtures of trimesic acid derivatives and to novel trimesic acid
derivatives.
[0003] Polypropylene resin is widely applied in a variety of areas
as the material of choice for film molding, sheet molding, blow
molding, injection molding, and the like, because of its excellent
processability and mechanical and electrical properties. Although
the resin has a number of very useful characteristics, its
crystallization behavior and optical properties are unattractive,
which result in restricting application of this material, in
particular in the packaging industry. Several attempts have been
made to improve the crystallizability, transmittance and clarity,
and reduce haze of polypropylene, notably by the addition of
nucleating agents and clarifiers.
[0004] Nucleating agents and clarifiers are commonly used in
industrial practice in combination with crystallizable
thermoplastic polymers to reduce processing cycle times or to
impart improved physico-chemical characteristics, such as various
optical, surface and mechanical properties, as well as to reduce
mold shrinkage. Elaborate lists of nucleating agents and clarifiers
can be found in, for example, U.S. Pat. No. 3,367,926, Plastics
Additives Handbook (4th Ed. Hanser, Munich, 1990, p. 863). Typical
nucleating agents known in the art are metallic salts of aliphatic
or aromatic carboxylic acids, aromatic salts, metallic salts of
aromatic phosphorus compounds, quinacridones, pigments, polymers
having melting points, highly branched polymers containing
dendritic branches (dendrimers), and minerals such as chalk,
gypsum, clay, kaolin, mica, talc and silicates, as well as
combinations thereof (U.S. Pat. No. 5,278,216, U.S. Pat. No.
5,137,973, U.S. Pat. No. 4,749,736, U.S. Pat. No. 4,694,064, U.S.
Pat. No. 4,338,228, U.S. Pat. No. 3,852,237; U. Johnsen and K.-H.
Moos, Angew. Makromol. Chem, vol. 74, p. 1 (1978); A. Wlochowicz
and M. Eder, Angew. Makromol. Chem, vol. 171, p. 79 (1989); H. N.
Beck, J. Appl. Polym. Sci., vol. 11, p. 673 (1967); F. L.
Binsbergen, Polymer, vol. 11, p. 253 (1970)). In addition,
DE-A-1,951,632 discloses the use of solid, crystalline aromatic
carboxilicimide-diphthalimides and N-substituted aromatic
carboxylic imide-diphthalimides.
[0005] More recently developed nucleating agents and clarifiers
dissolve in the polymer melt (R. Schlotmann and R. Walker,
Kunststoffe, vol. 86, p. 1002 (1996)), which was found to be
effective for improving dispersion of these additives. Most popular
have become compounds that are based on D-sorbitol, which belongs
to the general chemical family of carbohydrates, that is defined as
polyhydroxy aldehydes, polyhydroxy ketones, or compounds that can
be hydrolyzed to them (R. T. Morrion and Robert Neilson Boyd,
Organic Chemistry, 2nd. Ed., (Allyn and Bacon, Inc., Boston), 1966,
p. 983). There are several commercial nucleators based on sorbitol
including 1,3-2,4-di(benzylidene)-D-sorbitol (Millad 3905 (RTM),
Milliken Chemical Co. (RTM)); 1,3-2,4-di(4-tolylidene)-D-sorbitol
(Millad 3940 (RTM), Milliken Chemical Co. (RTM));
1,3-2,4-(3,4-dimethylbenzylidene)-D-sorbitol (Millad 3988 (RTM),
Milliken Chemical Co. (RTM));
1,3-2,4-di(4-ethylbenzylidene)-D-sorbitol (N-4, Mitsui
Petrochemical Industries, Ltd. (RTM)). U.S. Pat. No. 5,574,174,
U.S. Pat. No. 5,198,484 and WO-A-95/13317 disclose the preparation
and use of sorbitol derivatives. U.S. Pat. No. 4,294,747 discloses
polyhydric alcohol acetals of benzaldehyde and derivatives thereof.
U.S. Pat. No. 5,216,051 describes triacetal polyol compounds. Use
of dibenzylidene sorbitol (U.S. Pat. No. 4,016,118) in combination
with phenyl phosphate compounds is disclosed in U.S. Pat. No.
4,585,817. Despite wide-spread commercial application, there exist
a number of difficulties that are associated with
carbohydrate-based compounds as nucleating and clarifying agents.
First, the preparation and purification of sorbitol-based
nucleating agents is cumbersome. Another of the well-known
difficulties associated with the use of sorbitol clarifying agents
in, for example, polyolefins resins is the formation of small
bubbles in articles fabricated from these resins, which appear as
white points (U.S. Pat. No. 5,198,484). Finally, among other
disadvantages is their unsatisfactory temperature stability that is
inherent to this class of materials.
[0006] The above compounds are either ineffective in simultaneously
improving crystallizability and transmittance and clarity and haze
of polypropylene resin, or exhibit insufficient heat resistance
during processing, which is undesirable and may cause degradation
and/or sublimation of the additive and promote degradation of the
polymer.
[0007] Thus, a demand for further improvement of nucleating agents
and clarifiers continues to exist. JP-A-Hei 7/278,374 describes a
polypropylene resin composition containing tricarballytic acid-type
amide compounds and having high crystallization temperature and
improved transparency.
[0008] Several trimesic acid derivatives are known in the art, and
their use as nucleating agents for polypropylene resins has been
suggested for example in EP-A-940,431. Although principally
directed to enhancement of rigidity of polypropylene resin, in
JP-A-Hei06/192,496 it has been suggested that these compounds may
impart improved transparency. However, no mention is made or
suggested of improved transmittance or clarity or reduced haze,
which are entirely different properties, and not naturally and
necessarily are synonymous with improved transparency. As
background, it is noted that haze determines the turbidity, and
clarity the resolution or sharpness of the image of an object that
is placed behind a film or plaque of the resin, while transmittance
is associated with the amount of light that reaches the
observer.
[0009] It has not been taught in the art, which among the enormous
variety of trimesic acid derivatives known as nucleating agents for
polypropylene resins enhance the transmittance, which ones improve
clarity, which ones reduce haze and which compounds simultaneously
impart all of these highly desirable properties to
polypropylene.
[0010] The present invention relates in particular to
[0011] a polypropylene composition containing the components
[0012] a) a crystallizable polypropylene homopolymer, random
copolymer, alternating or segmented copolymer, block copolymer or a
blend of polypropylene with another synthetic polymer, and
[0013] b) 0.001 to 5%, relative to the weight of component a), of a
compound of the formula (I) ##STR1##
[0014] R.sub.1, R.sub.2 and R.sub.3, independently of one another,
are
[0015] C.sub.1-C.sub.20alkyl,
[0016] C.sub.1-C.sub.20alkyl substituted by
C.sub.1-C.sub.20alkylamino, di(C.sub.1-C.sub.20alkyl)amino,
C.sub.1-C.sub.20alkyloxy or hydroxy;
[0017] {poly(C.sub.2-C.sub.4alkoxy)}-(C.sub.2-C.sub.4alkyl),
[0018] C.sub.2-C.sub.20alkenyl,
[0019] C.sub.3-C.sub.12cycloalkyl,
[0020] C.sub.3-C.sub.12cycloalkyl substituted by 1, 2 or 3
C.sub.1-C.sub.20alkyl;
[0021] cyclohexylmethyl;
[0022] cyclohexylmethyl substituted by 1, 2 or 3
C.sub.1-C.sub.20alkyl;
[0023] C.sub.3-C.sub.12cycloalkenyl,
[0024] C.sub.3-C.sub.12cycloalkenyl substituted by 1, 2 or 3
C.sub.1-C.sub.20alkyl;
[0025] phenyl,
[0026] phenyl substituted by 1, 2 or 3 radicals selected from the
group consisting of C.sub.1-C.sub.20alkyl,
C.sub.1-C.sub.20alkyloxy, hydroxy, halogen, trihalogenmethyl,
trihalogenmethoxy, benzoyl, phenylamino, acylamino and
phenylazo;
[0027] phenyl substituted by 5 halogen,
[0028] C.sub.7-C.sub.9phenylalkyl,
[0029] C.sub.7-C.sub.9phenylalkyl which is substituted on the
phenyl by 1, 2 or 3 radicals selected from the group consisting of
C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.20alkoxy and hydroxy;
[0030] naphthyl,
[0031] naphthyl substituted by C.sub.1-C.sub.20alkyl;
[0032] adamantyl,
[0033] adamantyl substituted by C.sub.1-C.sub.20alkyl; or
[0034] a 5 to 6 membered heterocyclic group;
[0035] characterized in that the polypropylene composition has a
haze value which is smaller than 62%, preferably smaller than 40%;
the haze value being measured at a plate of 1.1-1.2 mm thickness.
In this case, the clarity determined as described in the working
examples is e.g. larger than 50%, preferably larger than 90%.
[0036] The polypropylene compositions according to the present
invention also show a high transmittance which means for example a
transmittance of more than 80% or 85%, preferably 80 to 98%, 85 to
92% or 83 to 95%.
[0037] The crystallization temperature of the polypropylene
composition according to the present invention is in general higher
than the crystallization temperature of a corresponding
polypropylene composition without component b).
[0038] Examples of C.sub.1-C.sub.20alkyl are methyl, ethyl, propyl,
isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl,
n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl,
1-methyl-hexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl,
1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl,
1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl,
undecyl, 1-methyl-undecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,
tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl
and eicosyl.
[0039] Preferred examples are isopropyl, n-butyl, sec-butyl,
tert-butyl, n-pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,
3-methylbutyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, tert-octyl
(1,1,3,3-tetramethylbutyl), isononyl, n-dodecyl, tridecyl or the
tallow alkyl mixture. Tert-butyl, 3-methylbutyl, 1,2-dimethylpropyl
and tert-octyl are particularly preferred.
[0040] Examples of C.sub.1-C.sub.20alkyl substituted by
C.sub.1-C.sub.20alkylamino, di(C.sub.1-C.sub.20alkyl)amino,
C.sub.1-C.sub.20alkyloxy or hydroxy are 3-methylaminopropyl,
2-dimethylaminoethyl, 2-diethylaminoethyl, 3-dimethylaminopropyl,
3-diethylaminopropyl, 2-methoxyethyl, 2-ethoxyethyl,
2-methoxypropyl, 2-ethoxypropyl, 3-isopropoxypropyl and
hydroxyethyl.
[0041] An example of
{poly(C.sub.2-C.sub.4alkoxy)}-(C.sub.2-C.sub.4alkyl) is
{polypropylene oxide}propyl.
[0042] Examples of C.sub.2-C.sub.20alkenyl are allyl, 2-methallyl,
butenyl, pentenyl, hexenyl and oleyl. The carbon atom in position 1
is preferably saturated. Particularly preferred examples are allyl
and oleyl.
[0043] Examples of C.sub.3-C.sub.12cycloalkyl are cyclopropyl,
cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and
cyclododecyl.
[0044] Preferred examples are cyclopentyl and cyclohexyl.
[0045] A preferred example of C.sub.3-C.sub.12cycloalkyl
substituted by 1, 2 or 3 C.sub.1-C.sub.20alkyl is
2-methylcyclohexyl.
[0046] An example of cyclohexylmethyl substituted by 1, 2 or 3
C.sub.1-C.sub.20alkyl is methylcyclohexylmethyl.
[0047] An example of C.sub.3-C.sub.12cycloalkenyl is
cyclohexenyl.
[0048] An example of C.sub.3-C.sub.12cycloalkenyl substituted by 1,
2 or 3 C.sub.1-C.sub.20alkyl is methylcyclohexenyl.
[0049] Examples of phenyl substituted by 1, 2 or 3 radicals
selected from the group consisting of C.sub.1-C.sub.20alkyl,
C.sub.1-C.sub.20alkyloxy, hydroxy, halogen, trihalogenmethyl,
trihalogenmethoxy, benzoyl, phenylamino, acylamino and phenylazo
are 4-methylphenyl, 2-ethylphenyl, 4-ethylphenyl,
4-isopropylphenyl, 4-tert-butylphenyl, 4-sec-butylphenyl,
4-isobutylphenyl, dodecylphenyl, 3,5-dimethylphenyl,
3,4-dimethylphenyl, 2,4-dimethylphenyl, 2,6-diethylphenyl,
2-ethyl-6-methylphenyl, 2,6-diisopropylphenyl, 4-methoxyphenyl,
4-ethoxyphenyl, 4-hydroxyphenyl, 4-fluorophenyl,
3,5-difluorophenyl, 2-chlorophenyl, 3-chlorophenyl,
3-chloro-6-methylphenyl, 3,5-di(trifluoromethyl)phenyl,
4-trifluoromethoxyphenyl, 2-benzoylphenyl, 4-phenylaminophenyl,
4-acetamidophenyl and 4-(phenylazo)phenyl.
[0050] Halogen is preferably fluorine or chlorine.
[0051] An example of phenyl substituted by 5 halogens is
pentafluorophenyl.
[0052] Examples of C.sub.7-C.sub.9phenylalkyl are benzyl and
2-phenylethyl.
[0053] Examples of C.sub.7-C.sub.9phenylalkyl which is substituted
on the phenyl by 1, 2 or 3 radicals selected from the group
consisting of C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.20alkoxy and
hydroxy are methylbenzyl, dimethylbenzyl, trimethylbenzyl,
tert-butylbenzyl, methoxybenzyl and
3,5-di-tert-butyl-4-hydroxybenzyl.
[0054] An example of naphthyl substituted by C.sub.1-C.sub.20alkyl
is methylnaphthyl.
[0055] An example of adamantyl substituted by C.sub.1-C.sub.20alkyl
is methyladamantyl.
[0056] Examples of a 5 to 6 membered heterocyclic group are
2-picolyl, (2-furyl)methyl, (2-tetrahydrofuryl)methyl, 2-pyrimidyl,
6-methyl-2-pyridyl, 1,2,4-triazol-3-yl and
2-(1-piperazinyl)ethyl.
[0057] The haze is determined according to ASTM D 1003. Haze is
defined as that percentage transmitted light which in passing
through a specimen (plate) deviates from the incident beam by more
than 2.5.degree. on the average. Clarity is evaluated in the angle
range smaller than 2.5.degree.. The specimen shall have
substantially plane-parallel surfaces free of dust, grease,
scratches, and blemishes, and it shall be free of distinct internal
voids and particles.
[0058] A polypropylene composition which is characterized by a haze
of 3 to 62% is preferred. In this case, the clarity determined as
described in the working examples is e.g. 50 to 99.9%, for example
60 to 99.9%, 70 to 99.9%, 80 to 99.9%, 90 to 99.9%, 95 to 99.9% or
95 to 99%.
[0059] A polypropylene composition which is characterized by a haze
of 3 to 50% is of further interest. In this case, the clarity
determined as described in the working examples is e.g. 80 to
99.9%, preferably 95 to 99.9% or 95 to 99%.
[0060] A polypropylene composition which is characterized by a haze
of 3 to 40% is particularly preferred. In this case, the clarity
determined as described in the working examples is e.g. 90 to
99.9%, preferably 95 to 99.9% or 95 to 99%.
[0061] A polypropylene composition which is characterized by a haze
of 25 to 40% is also of interest. In this case, the clarity
determined as described in the working examples is e.g. 95 to
99.9%, for example 95 to 99% or 97 to 99%.
[0062] Examples of haze are 3 to 55%, 3 to 50%, 3 to 45%, 3 to 40%,
3 to 35%, 3 to 30%, 5 to 55%, 5 to 50%, 5 to 45%, 5 to 40%, 5 to
35%, 5 to 30%, 7 to 55%, 7 to 50%, 7 to 45%, 7 to 40%, 7 to 35%, 7
to 30%, 10 to 55%, 10 to 50%, 10 to 45%, 10 to 40%, 10 to 35%, 10
to 30%, 15 to 55%, 15 to 50%, 15 to 45%, 15 to 40%, 15 to 35%, 15
to 30%, 20 to 55%, 20 to 50%, 20 to 45%, 20 to 40%, 20 to 35% and
20 to 30%. In this case, the clarity determined as described in the
working examples is e.g. 95 to 99.9%.
[0063] According to a preferred embodiment of the present invention
component a) is a polypropylene homopolymer.
[0064] Polypropylene homopolymer also covers long chain branched
polypropylene.
[0065] Polypropylene, can be prepared by different, and especially
by the following, methods:
[0066] Catalytic polymerization using a catalyst that normally
contains one or more than one metal of groups IVb, Vb, VIb or VIII
of the Periodic Table. These metals usually have one or more than
one ligand, typically oxides, halides, alcoholates, esters, ethers,
amines, alkyls, alkenyls and/or aryls that may be either .pi.- or
.sigma.-coordinated. These metal complexes may be in the free form
or fixed on substrates, typically on activated magnesium chloride,
titanium(III) chloride, alumina or silicon oxide. These catalysts
may be soluble or insoluble in the polymerisation medium. The
catalysts can be used by themselves in the polymerisation or
further activators may be used, typically metal alkyls, metal
hydrides, metal alkyl halides, metal alkyl oxides or metal
alkyloxanes, said metals being elements of groups Ia, IIa and/or
IIIa of the Periodic Table. The activators may be modified
conveniently with further ester, ether, amine or silyl ether
groups. These catalyst systems are usually termed Phillips,
Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene
or single site catalysts (SSC).
[0067] When component a) is a Ziegler-Natta homo polypropylene, the
polypropylene composition according to the present invention has
preferably a haze of 5 to 40% or 10 to 40%, in particular 15 to
40%, 20 to 40% or 25 to 40%. In this case, the clarity determined
according to the working examples is e.g. 90 to 99.9%, in
particular 90 to 99%, 95 to 99.9% or 95 to 99%.
[0068] When component a) is a Ziegler-Natta polypropylene
copolymer, the polypropylene composition according to the present
invention has preferably a haze of 4 to 40%, in particular 4 to
30%, 4 to 20% or 4 to 15%. In this case, the clarity determined
according to the working examples is e.g. 90 to 99.9%, in
particular 90 to 99%, 95 to 99.9% or 95 to 99%.
[0069] When component a) is a metallocene homo polypropylene, the
polypropylene composition according to the present invention has
preferably a haze of 5 to 30%, in particular 5 to 20%, 5 to 15% or
5 to 10%. In this case, the clarity determined according to the
working examples is e.g. 90 to 99.9%, in particular 90 to 99%, 95
to 99.9% or 95 to 99%.
[0070] When component a) is a metallocene polypropylene copolymer,
the polypropylene composition according to the present invention
has preferably a haze of 3 to 25%, in particular 3 to 20%, 3 to
15%, 3 to 10% or 3 to 8%. In this case, the clarity determined
according to the working examples is e.g. 90 to 99.9%, in
particular 90 to 99%, 95 to 99.9% or 95 to 99%.
[0071] According to a further preferred embodiment of the present
invention, component a) is a polypropylene random copolymer,
alternating or segmented copolymer or block copolymer containing
one or more comonomers selected from the group consisting of
ethylene, C.sub.4-C.sub.20-.alpha.-olefin, vinylcyclohexane,
vinylcyclohexene, C.sub.4-C.sub.20alkandiene,
C.sub.5-C.sub.12cycloalkandiene and norbornene derivatives; the
total amount of propylene and the comonomer(s) being 100%.
[0072] Polypropylene copolymer also covers long chain branched
polypropylene copolymer.
[0073] Examples of suitable C.sub.4-C.sub.20.alpha.-olefins are
1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,
1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene,
1-octadecene, 1-eicosene and 4-methyl-1-pentene.
[0074] Examples of suitable C.sub.4-C.sub.20alkandienes are
hexadiene and octadiene.
[0075] Examples of suitable C.sub.5-C.sub.12cycloalkandienes are
cyclopentadiene, cyclohexadiene and cyclooctadiene.
[0076] Examples of suitable norbornene derivatives are
5-ethylidene-2-norbornene (ENB), dicyclopentadiene (DCP) and
methylene-domethylene-hexahydronaphthaline (MEN).
[0077] A propylene/ethylene copolymer contains for example 50 to
99.9%, preferably 80 to 99.9%, in particular 90 to 99.9%, by weight
of propylene.
[0078] A propylene copolymer wherein the comonomer is a
C.sub.9-C.sub.20.alpha.-olefin such as e.g. 1-nonene, 1-decene,
1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene
or 1-eicosene; C.sub.9-C.sub.20alkandiene,
C.sub.9-C.sub.12cycloalkandiene or a norbornene derivative such as
e.g. 5-ethylidene-2-norbornene (ENB) or
methylene-domethylene-hexahydronaphthaline (MEN) contains
preferably more than 90 mol %, in particular 90 to 99.9 mol % or 90
to 99 mol %, of propylene.
[0079] A propylene copolymer wherein the comonomer is a
C.sub.4-C.sub.8.alpha.-olefin such as e.g. 1-butene, 1-pentene,
1-hexene, 1-heptene, 1-octene or 4-methyl-1-pentene;
vinylcyclohexane, vinylcyclohexene, C.sub.4-C.sub.8alkandiene or
C.sub.5-C.sub.8cycloalkandiene contains preferably more than 80 mol
%, in particular 80 to 99.9 mol % or 80 to 99 mol %, of
propylene.
[0080] Further examples of component a) are propylene/isobutylene
copolymer, propylene/butadiene copolymer, propylene/cycloolefin
copolymer, terpolymers of propylene with ethylene and a diene such
as hexadiene, dicyclopentadiene or ethylidene-norbornene;
propylene/1-olefin copolymers where the 1-olefin is generated in
situ; and propylene/carbon monoxide copolymers.
[0081] Other examples of component a) are blends of polypropylene
with propylene/ethylene copolymers, propylene/butylene copolymers,
polyethylene, e.g. HDPE or LDPE; polybutene, polyisobutylene,
poly-4-methylpentene or alternating or random polyalkylene/carbon
monoxide copolymers. These blends contain preferably at least 50%
by weight, relative to the weight of the total blend, of
polypropylene.
[0082] According to one of the preferred embodiments of the present
invention the radicals R.sub.1, R.sub.2 and R.sub.3 in the formula
(I) are identical.
[0083] Polypropylene compositions wherein R.sub.1 and R.sub.2 are
identical and R.sub.3 is different from R.sub.1 and R.sub.2 are
also preferred.
[0084] Of interest is a polypropylene composition wherein
[0085] R.sub.1, R.sub.2 and R.sub.3, independently of one another,
are
[0086] C.sub.1-C.sub.18alkyl,
[0087] C.sub.1-C.sub.10alkyl substituted by
C.sub.1-C.sub.4alkylamino, di(C.sub.1-C.sub.4alkyl)amino or
C.sub.1-C.sub.4alkyloxy;
[0088] {poly(C.sub.2-C.sub.4alkoxy)}-(C.sub.2-C.sub.4alkyl),
[0089] C.sub.3-C.sub.18alkenyl,
[0090] C.sub.5-C.sub.6cycloalkyl,
[0091] C.sub.5-C.sub.6cycloalkyl substituted by 1, 2 or 3
C.sub.1-C.sub.4alkyl;
[0092] cyclohexylmethyl;
[0093] cyclohexylmethyl substituted by 1, 2 or 3
C.sub.1-C.sub.4alkyl;
[0094] phenyl,
[0095] phenyl substituted by 1, 2 or 3 radicals selected from the
group consisting of C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkyloxy,
hydroxy, halogen, benzoyl, phenylamino,
C.sub.1-C.sub.4alkanoylamino and phenylazo;
[0096] benzyl,
[0097] benzyl which is substituted on the phenyl by 1, 2 or 3
radicals selected from the group consisting of
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy and hydroxy;
[0098] phenylethyl,
[0099] phenylethyl which is substituted on the phenyl by 1, 2 or 3
radicals selected from the group consisting of
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy and hydroxy;
[0100] naphthyl,
[0101] naphthyl substituted by C.sub.1-C.sub.4alkyl;
[0102] adamantyl,
[0103] adamantyl substituted by C.sub.1-C.sub.4alkyl; or
[0104] a 5 to 6 membered heterocyclic group.
[0105] Of further interest is a polypropylene composition
wherein
[0106] R.sub.1 and R.sub.2, independently of one another, are
[0107] C.sub.3-C.sub.8alkyl,
[0108] C.sub.5-C.sub.6cycloalkyl,
[0109] cyclohexylmethyl,
[0110] C.sub.5-C.sub.6cycloalkyl substituted by 1, 2 or 3
C.sub.1-C.sub.4alkyl; or
[0111] adamantyl.
[0112] Also of interest is a polypropylene composition wherein
[0113] R.sub.1, R.sub.2 and R.sub.3, independently of one another,
are
[0114] C.sub.3-C.sub.8alkyl,
[0115] C.sub.5-C.sub.6cycloalkyl,
[0116] cyclohexylmethyl,
[0117] C.sub.5-C.sub.6cycloalkyl substituted by 1, 2 or 3
C.sub.1-C.sub.4alkyl; or
[0118] adamantyl.
[0119] R.sub.1, R.sub.2 and R.sub.3 are preferably identical and
are
[0120] isopropyl, 2-methylpropyl, 1-ethylpropyl,
1,1-dimethylpropyl, 1,2-dimethylpropyl, n-butyl, 2-butyl,
tert-butyl, 3-methylbutyl, 1,1,3,3-tetramethylbutyl, cyclobutyl,
cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 4-methylcyclohexyl,
cyclohexylmethyl, 3,3,5-trimethylcyclohexyl or 1-adamantyl; in
particular isopropyl, 2-methylpropyl, 1,1-dimethylpropyl,
1,2-dimethylpropyl, 2-butyl, tert-butyl, 3-methylbutyl,
1,1,3,3-tetramethylbutyl, cyclopentyl, cyclohexyl,
2-methylcyclohexyl, cyclohexylmethyl or 1-adamantyl.
[0121] According to a further preferred embodiment of the present
invention
[0122] R.sub.1, R.sub.2 and R.sub.3 are identical and are
isopropyl, 2-butyl, tert-butyl, cyclopentyl, cyclohexyl,
2-methylcyclohexyl or 1-adamantyl.
[0123] According to another preferred embodiment of the present
invention
[0124] R.sub.1, R.sub.2 and R.sub.3 are identical and are
1,2-dimethylpropyl, tert-butyl, 3-methylbutyl,
1,1,3,3-tetramethylbutyl, cyclopentyl or cyclohexyl.
[0125] According to a particularly preferred embodiment of the
present invention
[0126] R.sub.1, R.sub.2 and R.sub.3 are identical and are
1,2-dimethylpropyl, 3-methylbutyl or cyclopentyl.
[0127] Component b) is preferably 0.01 to 5%, for example 0.01 to
2%, 0.05 to 1%, 0.1 to 1% or 0.15 to 1%, relative to the weight of
component a), of a compound of the formula (I).
[0128] A further preferred embodiment of the present invention
relates to a polypropylene composition containing as additional
component c) 0.001 to 5%, preferably 0.01 to 5%, relative to the
weight of component a), of a conventional nucleating agent.
[0129] Examples of conventional nucleating agents are
[0130] 1) Aromatic sorbitol acetals, for example [0131]
1,3:2,4-bis(benzylidene)sorbitol, commercially available as
Irgaclear D (RTM), Millad 3905 (RTM) and Gel All D (RTM). [0132]
1,3:2,4-bis(4-methylbenzylidene)sorbitol, commercially available as
Irgaclear DM (RTM), Millad 3940 (RTM), NC-6 (Mitsui (RTM)) and Gel
All MD (RTM). [0133] 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol,
commercially available as Millad 3988 (RTM). [0134]
1,3:2,4-bis(4-ethylbenzylidene)sorbitol, commercially available as
NC-4 (Mitsui (RTM))
[0135] 2) Nucleating agents based upon salts of phosphoric acid,
for example [0136]
2,2'-Methylen-bis-(4,6-di-tert-butylphenyl)phosphate, commercially
available as Adeka Stab NA11 (RTM) and Adeka Stab NA21 (RTM).
[0137] 3) Nucleating agents based upon salts of carboxylic acid,
for example sodium benzoate.
[0138] 4) Nucleating agents based upon carboxy aluminum-hydroxide,
for example aluminum hydroxy-bis[4-(tert-butyl)benzoate],
commercially available as Sandostab 4030 (RTM).
[0139] 5) Nucleating agents based upon salts of rosin/adiebetic
acid, for example [0140] Pinecrystal KM-1300 (RTM). [0141]
Pinecrystal KM-1600 (RTM).
[0142] 6) Other nucleating agents, for example Zinc (II)
monoglycerolate commercially available as Prifer 3888 (RTM) and
Prifer 3881 (RTM).
[0143] A further embodiment of the present invention is a method
for providing a resin with a haze value which is smaller than 62%;
the haze value being measured at a plate of 1.1-1.2 mm thickness;
said resin being selected from the group consisting of a
crystallizable polypropylene homopolymer, random copolymer,
alternating or segmented copolymer, block copolymer and a blend of
polypropylene with another synthetic polymer; which method
comprises incorporating into the resin 0.001 to 5%, relative to the
weight of the resin, of a compound of the formula (I) as defined
above.
[0144] Another embodiment of the present invention is the use of a
compound of the formula (I) as haze reducing agent for a
crystallizable polypropylene homopolymer, random copolymer,
alternating or segmented copolymer, block copolymer or a blend of
polypropylene with another synthetic polymer.
[0145] Here, a normalized haze value (Haze.sub.norm) is defined as
indicated below. Haze norm = Haze .times. .times. of .times.
.times. a .times. .times. polypropylene .times. .times. composition
.times. according .times. .times. to .times. .times. the .times.
.times. present .times. .times. invention Haze .times. .times. of
.times. .times. the .times. .times. corresponding polypropylene
.times. .times. composition .times. .times. without .times. .times.
component .times. .times. b ) ##EQU1##
[0146] Examples of Haze.sub.norm are 5 to 95%, 10 to 95%, 20 to
95%, 30 to 95%, 40 to 95%, 50 to 95%, 60 to 95%, 70 to 95%, 80 to
95%, 5 to 85%, 10 to 85%, 20 to 85%, 30 to 85%, 40 to 85%, 50 to
85%, 60 to 85%, 70 to 85%, 80 to 85%, 5 to 80%, 10 to 80%, 20 to
80%, 30 to 80%, 40 to 80%, 50 to 80%, 60 to 80%, 70 to 80%, 5 to
75%, 10 to 75%, 20 to 75%, 30 to 75%, 40 to 75%, 50 to 75%, 60 to
75%, 70 to 75%, 5 to 70%, 10 to 70%, 20 to 70%, 30 to 70%, 40 to
70%, 50 to 70%, 60 to 70%, 5 to 60%, 10 to 60%, 20 to 60%, 30 to
60%, 40 to 60%, 50 to 60%, 5 to 55%, 10 to 55%, 20 to 55%, 30 to
55%, 40 to 55%, 50 to 55%, 5 to 50%, 10 to 50%, 20 to 50%, 30 to
50%, 40 to 50%, 5 to 45% 10 to 45%, 20 to 45%, 30 to 45%, 40 to
45%, 5to 40%, 10 to 40%, 20 to 40%, 30 to 40%, 5 to 30%, 10 to 30%,
20 to 30%, 5 to 20% and 10 to 20%.
[0147] Haze.sub.norm is preferably 5 to 50%. Of particular interest
is a Haze.sub.norm of 40 to 80%.
[0148] Another object of the present invention is a novel mixture
containing the components
[0149] b-1) a compound of the formula (I) as defined above, and
[0150] b-2) a further compound of the formula (I) as defined
above;
[0151] the components b-1) and b-2) being different and the weight
ratio of the components b-1) to b-2) being 1:100 to 100:1, for
example 1:90 to 90:1, 1:80 to 80:1, 1:70 to 70:1, 1:60 to 60:1,
1:50 to 50:1, 1:40 to 40:1, 1:30 to 30:1, 1:20 to 20:1, 1:10 to
10:1, 1:5 to 5:1, 1:4 to 4:1, 1:3 to 3:1, 1:2 to 2:1 or 1:1.
[0152] This mixture may contain as additional component c) a
conventional nucleating agent as described above; the weight ratio
of the component c) to the sum of the components b-1) and b-2)
being 1:20 to 20:1, for example 1:10 to 10:1, 1:5 to 5:1, 1:4 to
4:1, 1:3 to 3:1,1:2 to 2:1 or 1:1.
[0153] A further object of the present invention is a novel mixture
containing the components
[0154] b-1) a compound of the formula (I) as defined above,
[0155] b-2) a further compound of the formula (I) as defined above,
and
[0156] b-3) an additional compound of the formula (I) as defined
above;
[0157] the components b-1), b-2) and b-3) being different, and the
weight ratio of the components b-1) to b-2) being 1:100 to 100:1,
for example 1:90 to 90:1, 1:80 to 80:1, 1:70 to 70:1, 1:60 to 60:1,
1:50 to 50:1, 1:40 to 40:1, 1:30 to 30:1, 1:20 to 20:1, 1:10 to
10:1,1:5 to 5:1, 1:4 to 4:1, 1:3 to 3:1, 1:2 to 2:1 or 1:1, and the
weight ratio of the component b-3) to the sum of the components
b-1) and b-2) being 1:20 to 20:1, for example 1:10 to 10:1, 1:5 to
5:1,1:4 to 4:1, 1:3 to 3:1, 1:2 to 2:1 or 1:1.
[0158] The latter mixture may contain as an additional component c)
a conventional nucleating agent as defined above; the weight ratio
of the component c) to the sum of the components b-1), b-2) and
b-3) being 1:20 to 20:1, for example 1:10 to 10:1,1:5 to 5:1,1:4 to
4:1, 1:3 to 3:1, 1:2 to 2:1 or 1:1.
[0159] Another object of the present invention is a mixture
containing the components
[0160] b) a compound of the formula (I), and
[0161] c) a conventional nucleating agent;
[0162] the weight ratio of the components b) and c) being 1:20 to
20:1, for example 1:10 to 10:1, 1:5 to 5:1, 1:4 to 4:1, 1:3 to 3:1,
1:2 to 2:1 or 1:1.
[0163] A further embodiment of the present invention relates to a
composition containing a synthetic polymer, wax, oil or a blend of
synthetic polymers and one of the novel mixtures described
above.
[0164] Examples of synthetic polymers, waxes, oils or blends of
synthetic polymers are
[0165] 1. Polymers of monoolefins and diolefins, for example
polypropylene, polyisobutylene, polybut-1-ene,
poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or
polybutadiene, as well as polymers of cycloolefins, for instance of
cyclopentene or norbornene, polyethylene (which optionally can be
crosslinked), for example high density polyethylene (HDPE), high
density and high molecular weight polyethylene (HDPE-HMW), high
density and ultrahigh molecular weight polyethylene (HDPE-UHMW),
medium density polyethylene (MDPE), low density polyethylene
(LDPE), linear low density polyethylene (LLDPE), (VLDPE) and
(ULDPE).
[0166] Polyolefins, i.e. the polymers of monoolefins exemplified in
the preceding paragraph, preferably polyethylene and polypropylene,
can be prepared by different, and especially by the following,
methods: [0167] a) radical polymerisation (normally under high
pressure and at elevated temperature). [0168] b) catalytic
polymerisation using a catalyst that normally contains one or more
than one metal of groups IVb, Vb, VIb or VIII of the Periodic
Table. These metals usually have one or more than one ligand,
typically oxides, halides, alcoholates, esters, ethers, amines,
alkyls, alkenyls and/or aryls that may be either .pi.- or
.sigma.-coordinated.
[0169] These metal complexes may be in the free form or fixed on
substrates, typically on activated magnesium chloride,
titanium(III) chloride, alumina or silicon oxide. These catalysts
may be soluble or insoluble in the polymerisation medium. The
catalysts can be used by themselves in the polymerisation or
further activators may be used, typically metal alkyls, metal
hydrides, metal alkyl halides, metal alkyl oxides or metal
alkyloxanes, said metals being elements of groups Ia, IIa and/or
IIIa of the Periodic Table. The activators may be modified
conveniently with further ester, ether, amine or silyl ether
groups. These catalyst systems are usually termed Phillips,
Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene
or single site catalysts (SSC).
[0170] 2. Mixtures of the polymers mentioned under 1), for example
mixtures of polypropylene with polyisobutylene, polypropylene with
polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of
different types of polyethylene (for example LDPE/HDPE).
[0171] 3. Copolymers of monoolefins and diolefins with each other
or with other vinyl monomers, for example ethylene/propylene
copolymers, linear low density polyethylene (LLDPE) and mixtures
thereof with low density polyethylene (LDPE), propylene/but-1-ene
copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene
copolymers, ethylene/hexene copolymers, ethylene/methylpentene
copolymers, ethylene/heptene copolymers, ethylene/octene
copolymers, ethylene/vinylcyclohexane copolymers,
ethylene/cycloolefin copolymers (e.g. ethylene/norbornene like
COC), ethylene/1-olefins copolymers, where the 1-olefin is
generated in-situ; propylene/butadiene copolymers,
isobutylene/isoprene copolymers, ethylene/vinylcyclohexene
copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl
methacrylate copolymers, ethylene/vinyl acetate copolymers or
ethylene/acrylic acid copolymers and their salts (ionomers) as well
as terpolymers of ethylene with propylene and a diene such as
hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures
of such copolymers with one another and with polymers mentioned in
1) above, for example polypropylene/ethylene-propylene copolymers,
LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic
acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or
random polyalkylene/carbon monoxide copolymers and mixtures thereof
with other polymers, for example polyamides.
[0172] 4. Hydrocarbon resins (for example C.sub.5-C.sub.9)
including hydrogenated modifications thereof (e.g. tackifiers) and
mixtures of polyalkylenes and starch.
[0173] Homopolymers and copolymers from 1.)-4.) may have any
stereostructure including syndiotactic, isotactic, hemi-isotactic
or atactic; where atactic polymers are preferred. Stereoblock
polymers are also included.
[0174] 5. Polystyrene, poly(p-methylstyrene),
poly(.alpha.-methylstyrene).
[0175] 6. Aromatic homopolymers and copolymers derived from vinyl
aromatic monomers including styrene, .alpha.-methylstyrene, all
isomers of vinyl toluene, especially p-vinyltoluene, all isomers of
ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene,
and vinyl anthracene, and mixtures thereof. Homopolymers and
copolymers may have any stereostructure including syndiotactic,
isotactic, hemi-isotactic or atactic; where atactic polymers are
preferred. Stereoblock polymers are also included.
[0176] 6a. Copolymers including aforementioned vinyl aromatic
monomers and comonomers selected from ethylene, propylene, dienes,
nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and
vinyl chloride or acrylic derivatives and mixtures thereof, for
example styrene/butadiene, styrene/acrylonitrile, styrene/ethylene
(interpolymers), styrene/alkyl methacrylate,
styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl
methacrylate, styrene/maleic anhydride,
styrene/acrylonitrile/methyl acrylate; mixtures of high impact
strength of styrene copolymers and another polymer, for example a
polyacrylate, a diene polymer or an ethylene/propylene/diene
terpolymer; and block copolymers of styrene such as
styrene/butadiene/styrene, styrene/isoprene/styrene,
styrene/ethylene/butylene/styrene or
styrene/ethylene/propylene/styrene.
[0177] 6b. Hydrogenated aromatic polymers derived from
hydrogenation of polymers mentioned under 6.), especially including
polycyclohexylethylene (PCHE) prepared by hydrogenating atactic
polystyrene, often referred to as polyvinylcyclohexane (PVCH).
[0178] 6c. Hydrogenated aromatic polymers derived from
hydrogenation of polymers mentioned under 6a.).
[0179] Homopolymers and copolymers may have any stereostructure
including syndiotactic, isotactic, hemi-isotactic or atactic; where
atactic polymers are preferred. Stereoblock polymers are also
included.
[0180] 7. Graft copolymers of vinyl aromatic monomers such as
styrene or .alpha.-methylstyrene, for example styrene on
polybutadiene, styrene on polybutadiene-styrene or
polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile
(or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and
methyl methacrylate on polybutadiene; styrene and maleic anhydride
on polybutadiene; styrene, acrylonitrile and maleic anhydride or
maleimide on polybutadiene; styrene and maleimide on polybutadiene;
styrene and alkyl acrylates or methacrylates on polybutadiene;
styrene and acrylonitrile on ethylene/propylene/diene terpolymers;
styrene and acrylonitrile on polyalkyl acrylates or polyalkyl
methacrylates, styrene and acrylonitrile on acrylate/butadiene
copolymers, as well as mixtures thereof with the copolymers listed
under 6), for example the copolymer mixtures known as ABS, MBS, ASA
or AES polymers.
[0181] 8. Halogen-containing polymers such as polychloroprene,
chlorinated rubbers, chlorinated and brominated copolymer of
isobutylene-isoprene (halobutyl rubber), chlorinated or
sulfo-chlorinated polyethylene, copolymers of ethylene and
chlorinated ethylene, epichlorohydrin homo- and copolymers,
especially polymers of halogen-containing vinyl compounds, for
example polyvinyl chloride, polyvinylidene chloride, polyvinyl
fluoride, polyvinylidene fluoride, as well as copolymers thereof
such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl
acetate or vinylidene chloride/vinyl acetate copolymers.
[0182] 9. Polymers derived from .alpha.,.beta.-unsaturated acids
and derivatives thereof such as polyacrylates and
polymethacrylates; polymethyl methacrylates, polyacrylamides and
polyacrylonitriles, impact-modified with butyl acrylate.
[0183] 10. Copolymers of the monomers mentioned under 9) with each
other or with other unsaturated monomers, for example
acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate
copolymers, acrylonitrile/alkoxyalkyl acrylate or
acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl
methacrylate/butadiene terpolymers.
[0184] 11. Polymers derived from unsaturated alcohols and amines or
the acyl derivatives or acetals thereof, for example polyvinyl
alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate,
polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or
polyallyl melamine; as well as their copolymers with olefins
mentioned in 1) above.
[0185] 12. Homopolymers and copolymers of cyclic ethers such as
polyalkylene glycols, polyethylene oxide, polypropylene oxide or
copolymers thereof with bisglycidyl ethers.
[0186] 13. Polyacetals such as polyoxymethylene and those
polyoxymethylenes which contain ethylene oxide as a comonomer;
polyacetals modified with thermoplastic polyurethanes, acrylates or
MBS.
[0187] 14. Polyphenylene oxides and sulfides, and mixtures of
polyphenylene oxides with styrene polymers or polyamides.
[0188] 15. Polyurethanes derived from hydroxyl-terminated
polyethers, polyesters or polybutadienes on the one hand and
aliphatic or aromatic polyisocyanates on the other, as well as
precursors thereof.
[0189] 16. Polyamides and copolyamides derived from diamines and
dicarboxylic acids and/or from aminocarboxylic acids or the
corresponding lactams, for example polyamide 4, polyamide 6,
polyamide 6/6, 6/10, 619, 6/12, 4/6, 12/12, polyamide 11, polyamide
12, aromatic polyamides starting from m-xylene diamine and adipic
acid; polyamides prepared from hexamethylenediamine and isophthalic
or/and terephthalic acid and with or without an elastomer as
modifier, for example poly-2,4,4,-trimethylhexamethylene
terephthalamide or poly-m-phenylene isophthalamide; and also block
copolymers of the aforementioned polyamides with polyolefins,
olefin copolymers, ionomers or chemically bonded or grafted
elastomers; or with polyethers, e.g. with polyethylene glycol,
polypropylene glycol or polytetramethylene glycol; as well as
polyamides or copolyamides modified with EPDM or ABS; and
polyamides condensed during processing (RIM polyamide systems).
[0190] 17. Polyureas, polyimides, polyamide-imides, polyetherimids,
polyesterimids, polyhydantoins and polybenzimidazoles.
[0191] 18. Polyesters derived from dicarboxylic acids and diols
and/or from hydroxycarboxylic acids or the corresponding lactones,
for example polyethylene terephthalate, polybutylene terephthalate,
poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene
naphthalate (PAN) and polyhydroxybenzoates, as well as block
copolyether esters derived from hydroxyl-terminated polyethers; and
also polyesters modified with polycarbonates or MBS.
[0192] 19. Polycarbonates and polyester carbonates.
[0193] 20. Polyketones.
[0194] 21. Polysulfones, polyether sulfones and polyether
ketones.
[0195] 22. Crosslinked polymers derived from aldehydes on the one
hand and phenols, ureas and melamines on the other hand, such as
phenol/formaldehyde resins, urea/formaldehyde resins and
melamine/formaldehyde resins.
[0196] 23. Drying and non-drying alkyd resins.
[0197] 24. Unsaturated polyester resins derived from copolyesters
of saturated and unsaturated dicarboxylic acids with polyhydric
alcohols and vinyl compounds as crosslinking agents, and also
halogen-containing modifications thereof of low flammability.
[0198] 25. Crosslinkable acrylic resins derived from substituted
acrylates, for example epoxy acrylates, urethane acrylates or
polyester acrylates.
[0199] 26. Alkyd resins, polyester resins and acrylate resins
crosslinked with melamine resins, urea resins, isocyanates,
isocyanurates, polyisocyanates or epoxy resins.
[0200] 27. Crosslinked epoxy resins derived from aliphatic,
cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g.
products of diglycidyl ethers of bisphenol A and bisphenol F, which
are crosslinked with customary hardeners such as anhydrides or
amines, with or without accelerators.
[0201] 28. Cellulose acetates, cellulose propionates and cellulose
butyrates, or the cellulose ethers such as methyl cellulose; as
well as rosins and their derivatives.
[0202] 29. Blends of the aforementioned polymers (polyblends), for
example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS,
PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates,
POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS,
PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO,
PBT/PC/ABS or PBT/PET/PC.
[0203] The above items 1 to 3 are preferred.
[0204] The resin compositions of the present invention may be
prepared by standard procedures, well known to those skilled in the
art, of compounding, such as mixing the prescribed components in a
conventional mixer and melting and kneading the mixture with a
single- or twin-screw extruder, or the like.
[0205] To the resin compositions of the present invention,
additional materials can be added in a concentration range that
does not adversely affect the beneficial effects of the invention.
These materials may include stabilizers, antioxidants,
antibacterial agents, ultraviolet absorbers, thermostabilizers,
light stabilizers, neutralizers, antistatic agents, antiblocking
agents, heavy metal inactivation agents, flame retardants,
lubricants, peroxides, hydrotalcite, foaming agents, elastomers,
processing aids, additional nucleating agents, and the like and
mixtures thereof.
[0206] More detailed examples of these conventional additives are
listed below.
[0207] 1. Antioxidants
[0208] 1.1. Alkylated monophenols, for example
2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol,
2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,
2,6-di-tert-butyl-4-isobutylphenol,
2,6-dicyclopentyl-4-methylphenol,
2-(.alpha.-methylcyclohexyl)-4,6-dimethylphenol,
2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,
2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are
linear or branched in the side chains, for example
2,6-di-nonyl-4-methylphenol,
2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol,
2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol,
2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures
thereof.
[0209] 1.2. Alkylthiomethylphenols, for example
2,4-dioctylthiomethyl-6-tert-butylphenol,
2,4-dioctylthiomethyl-6-methylphenol,
2,4-dioctylthiomethyl-6-ethylphenol,
2,6-di-dodecylthiomethyl-4-nonylphenol.
[0210] 1.3. Hydroquinones and alkylated hydroquinones, for example
2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone,
2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,
2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyphenyl stearate,
bis-(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.
[0211] 1.4. Tocopherols, for example .alpha.-tocopherol,
.beta.-tocopherol, .gamma.-tocopherol, .delta.-tocopherol and
mixtures thereof (vitamin E).
[0212] 1.5. Hydroxylated thiodiphenyl ethers, for example
2,2'-thiobis(6-tert-butyl-4-methylphenol),
2,2'-thiobis(4-octylphenol),
4,4'-thiobis(6-tert-butyl-3-methylphenol),
4,4'-thiobis(6-tert-butyl-2-methylphenol),
4,4'-thiobis-(3,6-di-sec-amylphenol),
4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.
[0213] 1.6. Alkylidenebisphenols, for example
2,2'-methylenebis(6-tert-butyl-4-methylphenol),
2,2'-methylenebis(6-tert-butyl-4-ethylphenol),
2,2'-methylenebis[4-methyl-6-(.alpha.-methylcyclohexyl)-phenol],
2,2'-methylenebis(4-methyl-6-cyclohexylphenol),
2,2'-methylenebis(6-nonyl-4-methylphenol),
2,2'-methylenebis(4,6-di-tert-butylphenol),
2,2'-ethylidenebis(4,6-di-tert-butyl-phenol),
2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol),
2,2'-methylenebis[6-(.alpha.-methyl-benzyl)-4-nonylphenol],
2,2'-methylenebis[6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylphenol],
4,4'-methy-lenebis(2,6-di-tert-butylphenol),
4,4'-methylenebis(6-tert-butyl-2-methylphenol),
1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,
2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,
1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,
1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane-
, ethylene glycol
bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate],
bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopenta-diene,
bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphe-
nyl]terephtha-late, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,
2,2-bis-(3,5-di-tert-butyl-4-hydroxyphe-nyl)propane,
2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,
1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
[0214] 1.7. O--, N-- and S-benzyl compounds, for example
3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether,
octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,
tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,
tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,
bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,
bis(3,5-di-tert-butyl-4-hydroxy-benzyl)sulfide,
isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
[0215] 1.8. Hydroxybenzylated malonates, for example
dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,
di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,
di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malona-
te,
bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hy-
droxybenzyl)malonate.
[0216] 1.9. Aromatic hydroxybenzyl compounds, for example
1,3,5-tris-(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-trimethylbenzene,
1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
[0217] 1.10. Triazine compounds, for example
2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triaz-
ine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-tri-
azine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-t-
riazine,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,
1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-tr-
iazine,
1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.
[0218] 1.11. Benzylphosphonates, for example
dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,
diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the
calcium salt of the monoethyl ester of
3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
[0219] 1.12. Acylaminophenols, for example 4-hydroxylauranilide,
4-hydroxystearanilide, octyl
N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
[0220] 1.13. Esters of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono-
or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,
i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene
glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0221] 1.14. Esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with
mono- or polyhydric alcohols, e.g. with methanol, ethanol,
n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis-(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;
3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dim-
ethylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane.
[0222] 1.15. Esters of
.beta.-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono-
or polyhydric alcohols, e.g. with methanol, ethanol, octanol,
octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,
1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0223] 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic
acid with mono- or polyhydric alcohols, e.g. with methanol,
ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0224] 1.17. Amides of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hy-drazide,
N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxami-
de (Naugarde.RTM. XL-1, supplied by Uniroyal).
[0225] 1.18. Ascorbic Acid (Vitamin C)
[0226] 1.19. Aminic antioxidants, for example
N,N'-di-isopropyl-p-phenylenediamine,
N,N'-di-sec-butyl-p-phenylenediamine,
N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine,
N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,
N,N'-bis(1-methylheptyl)-p-phenylenediamine,
N,N'-dicyclohexyl-p-phenylenediamine,
N,N'-diphenyl-p-phenylenediamine,
N,N'-bis(2-naphthyl)-p-phenylenediamine,
N-isopropyl-N'-phenyl-p-phenylenediamine,
N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine,
N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine,
N-cyclohexyl-N'-phenyl-p-phenylenediamine,
4-(p-toluenesulfamoyl)diphenylamine,
N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,
N-allyidiphenylamine, 4-isopropoxydiphenylamine,
N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,
N-phenyl-2-naphthylamine, octylated diphenylamine, for example
p,p'-di-tert-octyldiphenylamine, 4-n-butyl-aminophenol,
4-butyrylaminophenol, 4-nonanoylaminophenol,
4-dodecanoylaminophenol, 4-octadecanoylaminophenol,
bis(4-methoxyphenyl)amine,
2,6-di-tert-butyl-4-dimethylamino-methylphenol,
2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane,
1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenyl-amino)propane,
(o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine,
tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and
dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono-
and dialkylated nonyldiphenylamines, a mixture of mono- and
dialkylated dodecyldiphenylamines, a mixture of mono- and
dialkylated isopropyl/isohexyl-diphenylamines, a mixture of mono-
and dialkylated tert-butyldiphenylamines,
2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a
mixture of mono- and dialkylated
tert-butyl/tert-octylphenothiazines, a mixture of mono- and
dialkylated tert-octylphenothiazines, N-allylphenothiazine,
N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene,
N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine,
bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,
2,2,6,6-tetramethylpiperidin-4-one,
2,2,6,6-tetramethylpiperidin-4-ol.
[0227] 2. UV Absorbers and Light Stabilisers
[0228] 2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example
2-(2'-hydroxy-5'-methylphenyl)-benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole,
2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole,
2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole,
2-(3',5'-bis-(.alpha.,.alpha.-dimethylbenzyl)-2'-hydroxyphenyl)benzotriaz-
ole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chl-
oro-benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-
-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-b-
enzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazo-
le,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotr-
iazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxy--
phenyl)benzotriazole,
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotri-
azole,
2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-y-
lphenol]; the transesterification product of
2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotr-
iazole with polyethylene glycol 300; ##STR2## where
R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl,
2-[2'-hydroxy-3'-(.alpha.,.alpha.-dimethylbenzyl)-5'-(1,1,3,3-tetramethyl-
butyl)phenyl]-benzotriazole;
2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(.alpha.,.alpha.-dimethylb-
enzyl)-phenyl]benzotriazole.
[0229] 2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy,
4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,
4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
[0230] 2.3. Esters of substituted and unsubstituted benzoic acids,
for example 4-tert-butyl-phenyl salicylate, phenyl salicylate,
octylphenyl salicylate, dibenzoyl resorcinol,
bis(4-tert-butylbenzoyl)-resorcinol, benzoyl resorcinol,
2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate,
hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl
3,5-di-tert-butyl-4-hydroxybenzoate,
2-methyl-4,6-di-tert-butylphenyl
3,5-di-tert-butyl-4-hydroxybenzoate.
[0231] 2.4. Acrylates, for example ethyl
.alpha.-cyano-.beta.,.beta.-diphenylacrylate, isooctyl
.alpha.-cyano-.beta.,.beta.-diphenylacrylate, methyl
.alpha.-carbomethoxycinnamate, methyl
.alpha.-cyano-.beta.-methyl-p-methoxy-cinnamate, butyl
.alpha.-cyano-.beta.-methyl-p-methoxy-cinnamate, methyl
.alpha.-carbomethoxy-p-methoxycinnamate and
N-(.beta.-carbomethoxy-.beta.-cyanovinyl)-2-methylindoline.
[0232] 2.5. Nickel compounds, for example nickel complexes of
2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1
or 1:2 complex, with or without additional ligands such as
n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel
dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g.
the methyl or ethyl ester, of
4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes
of ketoximes, e.g. of 2-hydroxy-4-methylphenyl-undecylketoxime,
nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or
without additional ligands.
[0233] 2.6. Sterically hindered amines, for example
bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,
bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,
bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxy-
benzylmalonate, the condensate of
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid, linear or cyclic condensates of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine,
tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate-
, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),
4-benzoyl-2,2,6,6-tetramethylpiperidine,
4-stearyloxy-2,2,6,6-tetramethylpiperidine,
bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-bu-
tylbenzyl)-malonate,
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,
bis(1-octyl-oxy-2,2,6,6-tetramethylpiperidyl)sebacate,
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or
cyclic condensates of
N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of
2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl-)-1,3,5-tria-
zine and 1,2-bis(3-aminopropylamino)-ethane, the condensate of
2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-tri-
azine and 1,2-bis-(3-aminopropylamino)ethane,
8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-d-
ione,
3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,
3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,
a mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of
1,2-bis(3-aminopropylamino)ethane and
2,4,6-trichloro-1,3,5-triazine as well as
4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.
[136504-96-6]); a condensate of 1,6-hexanediamine and
2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and
4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.
[192268-64-7]);
N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,
N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane,
a reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane
and epichlorohydrin,
1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)-
ethene,
N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethy-
lenediamine, a diester of 4-methoxy-methylene-malonic acid with
1,2,2,6,6-pentamethyl-4-hydroxypiperidine,
poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,
a reaction product of maleic acid
anhydride-.alpha.-olefin-copolymer with
2,2,6,6-tetramethyl-4-aminopiperidine or
1,2,2,6,6-pentamethyl-4-aminopiperidine.
[0234] 2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide,
2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide,
2,2'-didodecyloxy-5,5'-di-tert-butoxanilide,
2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide,
2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with
2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and
p-methoxy-disubstituted oxanilides and mixtures of o- and
p-ethoxy-disubstituted oxanilides.
[0235] 2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example
2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-
,
2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
2,4-bis(2-hydroxy-4-propyl-oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazi-
ne,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazi-
ne,
2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tr-
iazine,
2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-d-
imethyl)-1,3,5-triazine,
2-[4-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimeth-
yl)-1,3,5-triazine,
2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(-
2,4-dimethylphenyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimeth-
ylphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,
2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,
2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine-
, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,
2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis-
(2,4-dimethylphenyl)-1,3,5-triazine.
[0236] 3. Metal deactivators, for example N,N'-diphenyloxamide,
N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl)hydrazine,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine,
3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl
dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl
bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide,
N,N'-bis(salicyloyl)oxalyl dihydrazide,
N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
[0237] 4. Phosphites and phosphonites, for example triphenyl
phosphite, diphenyl-alkyl phosphites, phenyl-dialkyl phosphites,
tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl
phosphite, distearyl-pentaerythritol diphosphite,
tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol
diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol
diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite,
bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,
diisodecyloxypentaerythritol diphosphite,
bis(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,
bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite,
tristearyl sorbitol triphosphite,
tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylene diphosphonite,
6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosph-
ocin, bis(2,4-di-tert-butyl-6-methylphenyl)-methyl phosphite,
bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,
6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosp-
hocin,
2,2',2''-nitrilo-[triethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biph-
enyl-2,2'-diyl)phosphite],
2-ethylhexyl(3,3',5,5-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite,
5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.
[0238] The following phosphites are especially preferred:
[0239] Tris(2,4-di-tert-butylphenyl)phosphite (Irgafoso.RTM. 168,
Ciba-Geigy), tris(nonylphenyl)phosphite, ##STR3##
[0240] 5. Hydroxylamines, for example N,N-dibenzylhydroxylamine,
N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,
N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,
N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,
N-hexadecyl-N-octadecylhydroxylamine,
N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine
derived from hydrogenated tallow amine.
[0241] 6. Nitrones, for example N-benzyl-alpha-phenyl-nitrone,
N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone,
N-lauryl-alpha-undecyl-nitrone,
N-tetradecyl-alpha-tridecyl-nitrone,
N-hexadecyl-alpha-pentadecyl-nitrone,
N-octadecyl-alpha-heptadecyl-nitrone,
N-hexadecyl-alpha-heptadecyl-nitrone,
N-ocatadecyl-alpha-pentadecyl-nitrone,
N-heptadecyl-alpha-heptadecyl-nitrone,
N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived from
N,N-dialkylhydroxylamine derived from hydrogenated tallow
amine.
[0242] 7. Thiosynergists, for example dilauryl thiodipropionate or
distearyl thiodipropionate.
[0243] 8. Peroxide scavengers, for example esters of
.beta.-thiodipropionic acid, for example the lauryl, stearyl,
myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt
of 2-mercaptobenzimidazole, zinc dibutyidithiocarbamate,
dioctadecyl disulfide, pentaerythritol
tetrakis(.beta.-dodecylmercapto)propionate.
[0244] 9. Polyamide stabilisers, for example copper salts in
combination with iodides and/or phosphorus compounds and salts of
divalent manganese.
[0245] 10. Basic co-stabilisers, for example melamine,
polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea
derivatives, hydrazine derivatives, amines, polyamides,
polyurethanes, alkali metal salts and alkaline earth metal salts of
higher fatty acids, for example calcium stearate, zinc stearate,
magnesium behenate, magnesium stearate, sodium ricinoleate and
potassium palmitate, antimony pyrocatecholate or zinc
pyrocatecholate.
[0246] 11. Conventional nucleating agents, for example, inorganic
substances, such as talcum, metal oxides, such as titanium dioxide
or magnesium oxide, phosphates, carbonates or sulfates of,
preferably, alkaline earth metals; organic compounds, such as mono-
or polycarboxylic acids and the salts thereof, e.g.
4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium
succinate or sodium benzoate; polymeric compounds, such as ionic
copolymers (ionomers). Especially preferred are
1,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol,
1,3:2,4-di(paramethyldibenzylidene)sorbitol, and
1,3:2,4-di(benzylidene)sorbitol.
[0247] 12. Other additives, for example plasticisers, lubricants,
rheology additives, catalysts, flow-control agents, optical
brighteners, flameproofing agents, antistatic agents and blowing
agents.
[0248] 13. Benzofuranones and indolinones, for example those
disclosed in U.S. Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S.
Pat. No. 5,175,312; U.S. Pat. No. 5,216,052; U.S. Pat. No.
5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839
or EP-A-0591102 or
3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butylbenzofuran-2-one,
5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]-benzofuran-2-one,
3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one]-
, 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,
3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,
3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one,
3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,
3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one.
[0249] The weight ratio of the above described component b) to the
conventional additive is preferably 1:100 to 100:1, for example
1:90 to 90:1,1:80 to 80:1, 1:70 to 70:1, 1:60 to 60:1, 1:50 to
50:1, 1:40 to 40:1, 1:30 to 30:1, 1:20 to 20:1, 1:10 to 10:1, 1:5
to 5:1, 1:4 to 4:1, 1:3 to 3:1, 1:2 to 2:1 or 1:1,
[0250] The resin compositions according to the present invention
can be advantageously used as resin materials for films, sheets,
bottles, syringes, ordinary utensils, automotive parts, containers,
parts for electrical appliances, fibers, nonwoven fabrics and the
like, and are conveniently molded by a method suitable for the
intended products, such as injection molding, extrusion molding,
blow molding, or the like. More details are given below.
[0251] Some compounds of the formula (I) are novel. Thus, a further
embodiment of the present invention relates to a compound of the
formula (IA) ##STR4##
[0252] wherein
[0253] R.sub.1 and R.sub.2, independently of one another, are
[0254] C.sub.1-C.sub.20alkyl,
[0255] C.sub.1-C.sub.20alkyl substituted by
C.sub.1-C.sub.20alkylamino, di(C.sub.1-C.sub.20alkyl)amino,
C.sub.1-C.sub.20alkyloxy or hydroxy;
[0256] {poly(C.sub.2-C.sub.4alkoxy)}-(C.sub.2-C.sub.4alkyl),
[0257] C.sub.2-C.sub.20alkenyl,
[0258] C.sub.3-C.sub.12cycloalkyl,
[0259] C.sub.3-C.sub.12cycloalkyl substituted by 1, 2 or 3
C.sub.1-C.sub.20alkyl;
[0260] cyclohexylmethyl;
[0261] cyclohexylmethyl substituted by 1, 2 or 3
C.sub.1-C.sub.20alkyl;
[0262] C.sub.3-C.sub.12cycloalkenyl,
[0263] C.sub.3-C.sub.12cycloalkenyl substituted by 1, 2 or 3
C.sub.1-C.sub.20alkyl;
[0264] phenyl,
[0265] phenyl substituted by 1, 2 or 3 radicals selected from the
group consisting of C.sub.1-C.sub.20alkyl,
C.sub.1-C.sub.20alkyloxy, hydroxy, halogen, trihalogenmethyl,
trihalogenmethoxy, benzoyl, phenylamino, acylamino and
phenylazo;
[0266] phenyl substituted by 5 halogen,
[0267] C.sub.7-C.sub.9phenylalkyl,
[0268] C.sub.7-C.sub.9phenylalkyl which is substituted on the
phenyl by 1, 2 or 3 radicals selected from the group consisting of
C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.20alkoxy and hydroxy;
[0269] naphthyl,
[0270] naphthyl substituted by C.sub.1-C.sub.20alkyl;
[0271] adamantyl,
[0272] adamantyl substituted by C.sub.1-C.sub.20alkyl; or
[0273] a 5 to 6 membered heterocyclic group; and
[0274] R.sub.3 is 2-ethylhexyl, 3-methyl-1-butyl,
3-(dimethylamino)propyl, 3-(diethylamino)propyl,
3-(methylamino)propyl, 2-(ethoxy)ethyl, 3-(methoxy)propyl,
3-(ethoxy)propyl, 2-picolyl, furfuryl, tetrahydrofurfuryl,
2-pyrimidinyl, 4-(phenylamino)phenyl, 4-isopropylphenyl,
2-ethylphenyl, 2,4-diethylphenyl, 2-ethyl-6-methylphenyl,
2,6-diisopropylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl,
1,2,4-triazol-3-yl or 4-(phenlyazo)phenyl.
[0275] R.sub.1, R.sub.2 and R.sub.3 are preferably identical.
[0276] Another embodiment of the present invention relates to a
compound of the formula (IB) ##STR5##
[0277] wherein
[0278] R.sub.1, R.sub.2 and R.sub.3 are identical and are
[0279] 3-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl,
3,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2-ethylphenyl,
4-n-butylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl,
4-(n-decyloxy)phenyl, cyclopropyl, cyclobutyl, cycloheptyl,
1-adamantyl, 3-methylcyclohexyl, 2,3-dimethylcyclohexyl,
3,3,5-trimethylcyclohexyl, S(+)-1-cyclohexylethyl,
R(+)-1-cyclohexylethyl, isopropyl, 1,1-dimethylpropyl,
1,2-dimethylpropyl, 2-butyl, 3-methylbutyl,
1,1,3,3-tetramethylbutyl, 3,5-difluorophenyl, pentafluorophenyl or
4-(trifluoromethoxy)phenyl; preferably 1,2-dimethylpropyl,
3-methylbutyl or 1,1,3,3-tetramethylbutyl.
[0280] Another preferred embodiment of the present invention is a
composition containing a synthetic polymer, wax, oil or a blend of
synthetic polymers and one of the novel compounds described
above.
[0281] The compounds of the formula (I) can be prepared in analogy
to known processes, for example by reacting an appropriate amine
with 1,3,5-benzenetricarboxylic acid trichloride as described for
example in the standard works such as Houben-Weyl, Methoden der
Organischen Chemie [Methods of Organic Chemistry], published by
Georg Thieme, Stuttgart), under reaction conditions which are
known. In carrying out these reactions, it is also possible to take
advantage of variants known per se which are not specifically
mentioned here. The starting substances can, if so desired also be
formed in situ, by not isolating them out of the reaction mixture
but immediately reacting them further to the compounds of the
formula (I). Working Examples A to C describe a representative
method of the preparation.
[0282] Examples of appropriate amines are:
[0283] isopropylamine,
[0284] n-butylamine,
[0285] sec-butylamine
[0286] tert-butylamine,
[0287] n-pentylamine,
[0288] 1,1-dimethylpropylamine,
[0289] 1,2-dimethylpropylamine,
[0290] 3-methylbutylamine,
[0291] n-hexylamine,
[0292] n-heptylamine,
[0293] n-octylamine,
[0294] 2-ethylhexylamine,
[0295] tert-octylamine(1,1,3,3-tetramethylbutylamine),
[0296] isononylamine,
[0297] n-dodecylamine,
[0298] tridecylamine,
[0299] tallowamine,
[0300] 2-dimethylaminoethylamine,
[0301] 2-diethylaminoethylamine,
[0302] 3-dimethylaminopropylamine,
[0303] 3-diethylaminopropylamine,
[0304] 3-methylaminopropylamine,
[0305] Jeffamine(polypropylene oxide),
[0306] 2-methoxyethylamine,
[0307] 2-ethoxyethylamine,
[0308] 2-methoxypropylamine,
[0309] 2-ethoxypropylamine,
[0310] 3-isopropoxypropylamine,
[0311] allylamine,
[0312] oleylamine,
[0313] cyclopentylamine,
[0314] cyclohexylamine,
[0315] 2-methylcyclohexylamine,
[0316] cyclohexylmethylamine,
[0317] 4-methylphenylamine (=4-methylaniline),
[0318] 2-ethylphenylamine (=2-ethylaniline),
[0319] 4-ethylphenylamine (=4-ethylaniline),
[0320] 4-isopropylphenylamine (=4-isopropylaniline),
[0321] 4-tert-butylphenylamine (=4-tert-butylaniline),
[0322] 4-sec-butylphenylamine (=4-sec-butylaniline),
[0323] 4-isobutylphenylamine (=4-isobutylaniline),
[0324] dodecylphenylamine (=dodecylaniline),
[0325] 3,5-dimethylphenylamine (=3,5-dimethylaniline),
[0326] 3,4-dimethylphenylamine (=3,4-dimethylaniline),
[0327] 2,4-dimethylphenylamine (=2,4-dimethylaniline),
[0328] 2,6-diethylphenylamine (=2,6-diethylaniline),
[0329] 2-ethyl-6-methylphenylamine (=2-ethyl-6-methylaniline),
[0330] 2,6-diisopropylphenylamine (=2,6-diisopropylaniline),
[0331] 4-methoxyphenylamine (=4-methoxyaniline),
[0332] 4-ethoxyphenylamine (=4-ethoxyaniline),
[0333] 4-hydroxyphenylamine (=4-hydroxyaniline),
[0334] 4-acetamidophenylamine (=4-acetamidoaniline),
[0335] 3-chlorophenylamine (=3-chloroaniline),
[0336] 2-chlorophenylamine (=2-chloroaniline),
[0337] 3-chloro-6-methylphenylamine,
[0338] 2-benzoylphenylamine (=2-benzoylaniline),
[0339] 4-phenylaminophenylamine,
[0340] 4-(phenylazo)phenylamine (=4-aminoazobenzene),
[0341] benzylamine,
[0342] 2-phenylethylamine,
[0343] 1-naphthylamine,
[0344] adamantylamine,
[0345] 2-picolylamine,
[0346] (2-furyl)methylamine,
[0347] (2-tetrahydrofuryl)methylamine,
[0348] 2-pyrimidylamine,
[0349] 6-methyl-2-pyridylamine,
[0350] 1,2,4-triazol-3-ylamine, and
[0351] 2-(1-piperazinyl)ethylamine.
[0352] The following examples describe the present invention in
greater detail.
[0353] Unless indicated otherwise, heretofore and hereinafter, all
parts and percentages are by weight and all temperatures are given
in degrees Celsius (.degree. C.). "Customary working up" means:
addition to water, filtration of precipitate, extracting with
organic solvent and/or purifying the product by crystallization
and/or chromatography.
EXAMPLE A
Preparation of the Compound of the Formula
[0354] ##STR6##
[0355] 3.74 g (33 mmol) 2-methylcyclohexylamine and 0.1 g dry LiCl
are added under inert atmosphere to 70 ml of dry
N-methylpyrrolidinone (NMP) and 15 ml of dry pyridine and cooled to
5.degree. C. Then, 2.39 g (9 mmol) 1,3,5-benzenetricarboxylic acid
trichloride is added. The reaction mixture is heated to 75.degree.
C. and stirred. After 2 hours the reaction mixture is added to 300
ml of ice water. The precipitate is filtered off. Customary work-up
(recrystallization) gives 1,3,5-benzenetricarboxylic acid
tris(2-methylcyclohexylamide).
[0356] Yield: 2.68 g (5.41 mmol): 60.1%.
[0357] Melting Point: 414.degree. C. (under simultaneous
evaporation).
[0358] .sup.1H-NMR (DMSO-d.sub.6): .delta.=0.82-0.96 (2t, 9H);
0.98-1.88 (m, 27H); 3.45-3.60 and 4.01-4.17 (2m 3H); 8.16-8.33 (m,
3H); 8.42 (d,J=8.3 Hz, 3H).
[0359] .sup.13C-NMR (CF.sub.3COOD/CDCl.sub.3 1:1): .delta.=15.2;
18.7; 22.5; 22.7; 25.3; 25.5; 28.7; 30.0; 32.8; 33.5; 34.3; 37.7;
53.3; 57.6; 130.7; 134.2; 168.2; 168.4; 168.6; 168.8.
[0360] IR (KBr, cm.sup.-1): 3226; 3060; 2929; 1637; 1555; 1250.
[0361] MS (70 eV). m/z (mass spectroscopy): 495 (M.sup.+, 5%).
EXAMPLE B
Preparation of the Compound of the Formula
[0362] ##STR7##
[0363] 0.93 g (10 mmol) aniline and 0.1 g dry LiCl are added under
inert atmosphere to 50 ml of dry NMP and 5 ml of dry pyridine and
cooled to 5.degree. C. 0.80 g (mmol) 1,3,5-benzenetricarboxylic
acid trichloride is added. Then, the reaction mixture is heated to
75.degree. C. and stirred. After 2 hours the reaction mixture is
added to 100 ml of ice water. The precipitate is filtered off.
Customary work-up (Soxhlet extraction) gives
1,3,5-benzenetricarboxylic acid tris(phenylamide).
[0364] Yield: 0.80 g (1.8 mmol): 61.2%.
[0365] Melting point: 312.degree. C.
[0366] .sup.1H-NMR (DMSO-d.sub.6): .delta.=7.14 (t, J=7.2 Hz, 3H);
7.40 (dd, J.sub.1=8.5 Hz, J.sub.2=7.2 Hz, 6H); 7.82 (d, J=8.5 Hz,
6H); 8.71 (s, 3H); 10.59 (s, 3H).
[0367] .sup.13C-NMR (CF.sub.3COOD/CDCl.sub.3 1:1): .delta.=122.8;
127.6; 129.7; 131.3; 135.2; 135.9; 167.5.
[0368] IR (KBr, cm.sup.-1): 3290; 3062; 1648; 1523; 1254.
[0369] MS (70 eV), m/z: 435 (M.sup.+, 84%).
EXAMPLE C
Preparation of the Compound of the Formula
[0370] ##STR8##
[0371] 0.99 g (10 mmol) cyclohexylamine and 0.1 g dry LiCl are
added under inert atmosphere to 30 ml of dry NMP and 5 ml of dry
pyridine and cooled to 5.degree. C. Then, 0.80 9 (3 mmol)
1,3,5-benzenetricarboxylic acid trichloride is added. The reaction
mixture is heated to 75.degree. C. and stirred. After 2 hours the
reaction mixture is added to 100 ml of ice water. The precipitate
is filtered off. Customary work-up (recrystallization) gives
1,3,5-benzenetricarboxylic acid tris(cyclohexylamide).
[0372] Yield: 0.85 g (1.9 mmol): 62.5%.
[0373] Melting point: 371.degree. C. (under simultaneous
evaporation).
[0374] .sup.1H-NMR (DMSO-d.sub.6): .delta.=1.01-2.05 (m, 30H); 3.78
(m, 3H); 8.28 (s, 3H); 8.43 (d, J=7.9 Hz, 3H).
[0375] .sup.13C-NMR (CF.sub.3COOD/CDCl.sub.3 1:1): .delta.=24.9;
25.2; 32.3; 51.8; 130.7; 134.3; 168.0.
[0376] IR (KBr, cm.sup.-1): 3264; 3077; 2932; 1650; 1542; 1258.
[0377] MS (70 eV). m/z: 453 (M.sup.+, 46%).
[0378] The following compounds characterized by their melting
points (m.p.) are analogously prepared. The melting point is
determined in a combined TGA/DSC-instrument at a heating rate of 10
K/min. [0379] Compound I-1: 1,3,5-benzenetricarboxylic acid
tris(3-methylbutylamide); m.p.=263.degree. C.**.sup.) [0380]
Compound I-2: 1,3,5-benzenetricarboxylic acid
tris(cyclopentylamide); m.p.=388.degree. C.**.sup.) [0381] Compound
I-3: 1,3,5-benzenetricarboxylic acid
tris(1,2-dimethylpropylamide);*.sup.) [0382] Compound I-4:
1,3,5-benzenetricarboxylic acid tris(cyclohexylamide);
m.p.=376.degree. C.**.sup.) [0383] Compound I-5:
1,3,5-benzenetricarboxylic acid tris(tert-octylamide);
m.p.=315.degree. C.**.sup.) [0384] Compound I-6:
1,3,5-benzenetricarboxylic acid
tris(1,1-dimethylpropylamide);*.sup.) [0385] Compound I-7:
1,3,5-benzenetricarboxylic acid tris(tert-butylamide);*.sup.)
[0386] Compound I-8: 1,3,5-benzenetricarboxylic acid
tris(cyclohexylmethylamide); m.p.=313.degree. C. [0387] Compound
I-9: 1,3,5-benzenetricarboxylic acid tris(isobutylamide);
m.p.=292.degree. C.**.sup.) [0388] Compound I-10:
1,3,5-benzenetricarboxylic acid tris(2-methylcyclohexylamide);
m.p.=414.degree. C.**.sup.) [0389] Compound I-11:
1,3,5-benzenetricarboxylic acid
tris(1,1-dimethylpropylamide);*.sup.) [0390] Compound I-12:
1,3,5-benzenetricarboxylic acid tris(isopropylamide);*.sup.) [0391]
Compound I-13: 1,3,5-benzenetricarboxylic acid
tris(2-butylamide);*.sup.) [0392] Compound I-14:
1,3,5-benzenetricarboxylic acid tris(1-adamantylamide);*.sup.)
[0393] Compound I-15: 1,3,5-benzenetricarboxylic acid
tris(1-ethylpropylamide); m.p.=378.degree. C.**.sup.) [0394]
Compound I-16: 1,3,5-benzenetricarboxylic acid
tris(3,3,5-trimethylcyclohexylamide);*.sup.) [0395] Compound I-17:
1,3,5-benzenetricarboxylic acid
tris(4-methylcyclohexylamide);*.sup.) [0396] Compound I-18:
1,3,5-benzenetricarboxylic acid tris(cyclobutylamide);
m.p.=329.degree. C.**.sup.) [0397] Compound I-19:
1,3,5-benzenetricarboxylic acid tris(n-butylamide);
m.p.=239.degree. C. [0398] Compound I-20:
1,3,5-benzenetricarboxylic acid tris(4-tert-butylphenylamide);
m.p.=334.degree. C. [0399] Compound I-21:
1,3,5-benzenetricarboxylic acid
tris(4-(trifluoromethoxy)phenylamide); m.p.=253.degree. C. [0400]
Compound I-22: 1,3,5-benzenetricarboxylic acid
tris(pentafluorophenylamide);*.sup.) [0401] Compound I-23:
1,3,5-benzenetricarboxylic acid tris(2-ethylphenylamide);
m.p.=309.degree. C. [0402] Compound I-24:
1,3,5-benzenetricarboxylic acid tris(2,4-dimethylphenylamide);
m.p.=298.degree. C. [0403] Compound I-25:
1,3,5-benzenetricarboxylic acid
tris(3,5-bis(triflouromethyl)phenylamide); m.p.=331.degree. C.
[0404] Compound I-26: 1,3,5-benzenetricarboxylic acid
tris(4-n-butylphenylamide); m.p.=232.degree. C. [0405] Compound
I-27: 1,3,5-benzenetricarboxylic acid tris(cycloheptylamide);
m.p.=394.degree. C.**.sup.) [0406] Compound I-28:
1,3,5-benzenetricarboxylic acid tris(R(-)-1-cyclohexylethylamide);
m.p.=392.degree. C.**.sup.) [0407] Compound I-29:
1,3,5-benzenetricarboxylic acid tris(2,4,6-trimethylphenylamide);
m.p.=369.degree. C.***.sup.) [0408] Compound I-30:
1,3,5-benzenetricarboxylic acid tris(4-methylphenylamide);
m.p.=303.degree. C. [0409] Compound I-31:
1,3,5-benzenetricarboxylic acid tris(benzylamide); m.p.=242.degree.
C.**.sup.) [0410] Compound I-32: 1,3,5-benzenetricarboxylic acid
tris(cyclopropylamide);*.sup.) [0411] Compound I-33:
1,3,5-benzenetricarboxylic acid tris(4-ethoxyphenylamide);
m.p.=266.degree. C. [0412] Compound I-34:
1,3,5-benzenetricarboxylic acid tris(3-methylphenylamide);
m.p.=252.degree. C. [0413] Compound I-35:
1,3,5-benzenetricarboxylic acid tris(phenylamide); m.p.=312.degree.
C. [0414] Compound I-36: 1,3,5-benzenetricarboxylic acid
tris(4-methoxyphenylamide); m.p.=277.degree. C. [0415] Compound
I-37: 1,3,5-benzenetricarboxylic acid
tris(2,3-dimethylphenylamide); m.p.=403.degree. C.***.sup.) [0416]
Compound I-38: 1,3,5-benzenetricarboxylic acid
tris(3,5-difluorophenylamide); m.p.=333.degree. C. [0417] Compound
I-39: 1,3,5-benzenetricarboxylic acid tris(4-fluorophenylamide);
m.p.=311.degree. C. [0418] Compound I-40:
1,3,5-benzenetricarboxylic acid tris(methylamide); m.p.=333.degree.
C.**.sup.) [0419] Compound I-41: 1,3,5-benzenetricarboxylic acid
tris(cyclododecylamide); m.p.=387**.sup.) [0420] Compound I-42:
1,3,5-benzenetricarboxylic acid tris(2-methylphenylamide);
m.p.=377***.sup.) [0421] Compound I-43: 1,3,5-benzenetricarboxylic
acid tris(3,5-dimethylphenylamide); m.p.=302.degree. C. [0422]
Compound I-44: 1,3,5-benzenetricarboxylic acid
tris(3,4-dimethylphenylamide);*.sup.) [0423] Compound I-45:
1,3,5-benzenetricarboxylic acid
tris(3-methylcyclohexylamide);*.sup.) [0424] Compound I-46:
1,3,5-benzenetricarboxylic acid tris(cyclooctylamide);*.sup.)
[0425] Compound I-47: 1,3,5-benzenetricarboxylic acid
tris(2,3-dimethylcyclohexylamide);*.sup.) [0426] Compound I-48:
1,3,5-benzenetricarboxylic acid tris(S(+)-1-cyclohexylethylamide);
m.p.=397.degree. C.**.sup.)
[0427] *) No melting before sublimation/decomposition.
[0428] **) Melting with simultaneous evaporation under 100% weight
loss.
[0429] ***) Melting under decomposition.
[0430] The general procedures used in the Working Examples 1 to 4
are described below.
[0431] Mixing Procedure:
[0432] To 59.91 g of powdered polypropylene (ELF-Atochem (RTM);
Appryl 3030BN1(RTM)) 90 mg of a powdered additive (0.15% by weight)
or a powdered mixture of additives (total 0.15% by weight) is
added, and tumble-mixed for 24 h in a glass container. In general,
4.5 g of this mixture are compounded at 239.degree. C. in a
small-scale, laboratory twin-screw, recirculating and corotating
extruder, for example the MicroCompounder of DACA Instruments
(RTM), for a period of about 4 min at a screw speed of 40 rpm, and
subsequently collected at room temperature. The neat polypropylene
is similarly treated to produce a blank control sample.
[0433] Differential Scanning Calorimetry (DSC):
[0434] A Perkin-Elmer DSC instrument (RTM) (Model DSC 7), operated
in a dry nitrogen atmosphere, is used for the analysis of the
crystallization behavior of the various mixtures and control
samples, according to standard procedures. About 5 to 10 mg of
sample is sealed into an aluminum cup, heated from 130.degree. C.
to 230.degree. C. at a rate of 10.degree. C./min, held at
230.degree. C. for 5 min, and then subsequently cooled at a rate of
10.degree. C./min to 50.degree. C. The data represented as
crystallization temperatures are the peak temperatures of the
exotherms in the thermograms that are recorded upon cooling.
[0435] Thermo-Gravimetric Analysis (TGA), Differential Thermal
Analysis (DTA):
[0436] An automated Netzsch TGA/DTA instrument (STA 409) (RTM)
operated in nitrogen is used for the analysis of the thermal
stability and the melting temperature. As melting temperatures the
peak maximum of the endothermic transition are presented. About 10
mg of sample is placed into an aluminum oxide crucible and heated
from 50.degree. C. to 640.degree. C. at a rate of 10.degree.
C./min.
[0437] Injection Molding:
[0438] The injection molding is performed with a MicroInjector
(DACA Instruments (RTM)). About 3.0 g of the pelletized thread is
placed under a nitrogen blanket in the barrel at 260.degree. C.
After the granulate is completely molten, the melt is injected into
a polished mold with a pressure of about 8 bar. The mold
temperature is 20.degree. C. The collected test specimen has a
diameter of 2.5 cm and a thickness of about 1.1-1.2 mm.
[0439] Optical Characterization (Transmission, Clarity, Haze):
[0440] Transmission, clarity and haze are measured with a haze-gard
plus instrument (BYK, Gardner (RTM), illumination CIE-C) at room
temperature. The haze-gard plus instrument conforms to ASTM D-1003.
The transmission, clarity and haze values are measured between
12-24 hours after obtaining the samples by injection molding.
EXAMPLE 1
[0441] 0.15 wt % of the compound of the formula (I) with R.sub.1,
R.sub.2 and R.sub.3 as indicated in Table 1 are added to the
polypropylene resin, processed and characterized according to the
above methods.
[0442] The crystallization temperature (T.sub.cryst.), haze,
clarity and transmission of the polypropylene composition according
to the present invention are listed in Table 1 as well as the
thickness of the test specimen (plate). TABLE-US-00001 TABLE 1
Compound T.sub.cryst. Thickness Clarity Haze Transmission No.
R.sub.1, R.sub.2, R.sub.3 [.degree. C.] [mm] [%] [%] [%] none 112.0
1.19 79.0 64.0 91.4 I-1 3-Methylbutyl 121.3 1.12 98.7 27.4 90.9 I-2
Cyclopentyl 121.0 1.11 97.8 28.8 88.4 I-3 1,2-Dimethylpropyl 124.7
1.12 98.2 30.0 91.0 I-4 Cyclohexyl 124.8 1.12 97.6 34.5 90.6 I-5
1,1,3,3-Tetramethylbutyl 124.3 1.11 98.9 35.8 88.8 I-6
1,1-Dimethylpropyl 126.7 1.13 97.7 36.2 87.9 I-7 tert-Butyl 128.7
1.10 97.9 36.2 86.6 I-8 Cyclohexylmethyl 123.0 1.12 98.8 36.6 90.2
I-9 2-Methylpropyl (Isobutyl) 118.2 1.08 98.5 37.1 91.6 I-10
2-Methylcyclohexyl 125.0 1.12 97.6 37.2 87.1 I-11
1,1-Dimethylpropyl 126.5 1.11 97.7 38.2 90.8 I-12 Isopropyl 125.2
1.13 97.2 38.6 89.6 I-13 2-Butyl 124.9 1.14 97.3 39.9 90.9 none
112.0 1.19 79.0 64.0 91.4 I-14 1-Adamantyl 127.4 1.13 97.0 40.0
88.6 I-15 1-Ethylpropyl 124.2 1.10 96.3 42.2 91.1 I-16
3,3,5-Trimethylcyclohexyl 122.3 1.11 94.7 44.5 87.4 I-17
4-Methylcyclohexyl 113.8 1.11 96.8 47.1 89.8 I-18 Cyclobutyl 114.0
1.13 95.8 52.4 89.9 I-19 n-Butyl 118.0 1.17 95.8 57.9 90.1 I-20
4-Tert-butylphenyl 127.0 1.17 94.8 60.6 90.1 I-21
4-(trifluoromethoxy)phenyl 110.5 1.14 85.4 60.7 89.6
EXAMPLE 2
[0443] 0.15 wt % of a 1:1 mixture of the compounds of the formula
(I) as indicated in Table 2 is added to polypropylene resin,
processed and characterized according to the methods described
above.
[0444] The crystallization temperature (T.sub.cryst.), haze,
clarity and transmission of the polypropylene composition according
to the present invention are listed in Table 2 as well as the
thickness of the test specimen (plate). TABLE-US-00002 TABLE 2
Thick- Trans- Mixture Compounds (1:1 T.sub.cryst. ness Clarity Haze
mission No. weight ratio) [.degree. C.] [mm] [%] [%] [%] none 112.0
1.19 79.0 64.0 91.4 2a Compounds I-2 123.6 1.15 97.1 34.5 91.3 and
I-10 2b Compounds I-7 125.5 1.15 98.1 30.9 88.3 and I-10 2c
Compounds I-2 125.2 1.12 97.7 32.7 90.7 and I-7 2d Compounds I-2
125.0 1.11 97.4 34.3 89.8 and I-4 The results in the above table
illustrate that binary mixtures of compounds of the formula (I),
when added to polypropylene resin, may further improve the
transmission (mixtures 2a to 2c) and/or clarity (mixtures 2b and
2d) and/or reduce haze (mixture 2b), when compared with the resin
comprising only one compound of the formula (I).
EXAMPLE 3
[0445] 0.15 wt % of a 1:1:1 mixture of the compounds of the formula
(I) as listed in Table 3 is added to polypropylene resin, processed
and characterized according to the above methods.
[0446] The crystallization temperature (T.sub.cryst), haze, clarity
and transmission of the polypropylene composition according to the
present invention are listed in Table 3 as well as the thickness of
the test specimen (plate). TABLE-US-00003 TABLE 3 Thick- Trans-
Mixture Compounds (1:1:1 T.sub.cryst. ness Clarity Haze mission No.
weight ratio) [.degree. C.] [mm] [%] [%] [%] none 112.0 1.19 79.0
64.0 91.4 3a Compounds I-2, 122.6 1.15 97.4 38.6 90.2 I-7 and I-10
3b Compounds I-2, 125.4 1.14 97.1 35.3 90.9 I-4 and I-10 3c
Compounds I-2, 123.3 1.15 98.4 29.1 90.6 I-4 and I-7 The results in
the above table illustrate that ternary mixtures of compounds of
the formula (I), when added to polypropylene resin, may even
further improve the transmission (mixtures 3a and 3b), and/or
clarity (mixture 3c) and/or reduce haze (mixture 3b) when compared
with resin comprising only one or two compounds of the formula
(I).
EXAMPLE 4
[0447] The thermal stability of the compounds indicated in Table 4
is determined by thermo-gravimetric analysis (TGA), according to
the procedure described above. The results are listed in the table
below. TABLE-US-00004 TABLE 4 Weight loss Compound Onset 5% 10% I-2
340.degree. C. 375.degree. C. 385.degree. C. I-4 334.degree. C.
372.degree. C. 384.degree. C. I-14 316.degree. C. 382.degree. C.
458.degree. C. I-10 361.degree. C. 407.degree. C. 412.degree. C.
I-12 308.degree. C. 341.degree. C. 355.degree. C. I-13 317.degree.
C. 347.degree. C. 358.degree. C. I-7 332.degree. C. 355.degree. C.
365.degree. C.
[0448] The data shown above illustrate the excellent thermal
stability of the compounds of the formula (I).
* * * * *